methods for ether synthesis are overwhelmingly 
 based upon the attack 
 of nucleophilic oxygen on electrophilic carbon . our lab has been interested in 
 expanding the scope of an umpoled strategy based upon reaction of 
 carbanions with electrophilic oxygen . the 
 reaction of dialkyl peroxides with carbanions , while long known , has largely remained a curiosity applied mainly 
 to transfer of methoxyl and other unhindered alkoxides . even a slight increase in steric bulk results in reduced yields , and reactions of di - t - butyl 
 peroxide furnish multiple products . we became 
 interested in a general method for selective transfer of 1 , 
 2 , or 3 alkoxides from a mixed peroxide to a carbanion . in approaching this problem , we were encouraged by evidence for the 
 strong influence of substituent groups on peroxide reactivity . bistrimethylsilyl 
 peroxide efficiently transfers osime3 to a variety of organometallic 
 reagents ; curiously , tbuoosime3 transfers neither osime3 nor tbuo . oxenoid  in character , transfer 
 lio to a variety of carbanions , and similar 
 reactivity patterns have been observed with other metalloperoxides . the strain within bicyclic peroxides 
 has been harnessed to facilitate reaction of more hindered peroxides ; 
 unfortunately , the presence of the scaffold limits the range of potential 
 targets . electronic activation in the 
 form of peresters has been employed to achieve transfer of tertiary 
 alkoxides to grignard reagents , but broad 
 application is limited by the propensity of peresters to undergo c - to - o rearrangement or fragmentation to carbonyls . we were particularly intrigued by reports describing enhanced reactivity 
 of acyclic peroxyacetals and peroxyaminals with grignard reagents . however , the reactions of peroxyaminals displayed variable regioselectivity , while reactions of a mixed ethoxy / peroxy acetal 
 required a significant excess of the grignard reagent . in preliminary work , we discovered that tetrahydropyranyl 
 ( thp ) monoperoxyacetals selectively transfer the attached or to lithiated 
 1,3-dithianes . we now describe investigations 
 of reactions between carbanions and several classes of organic peroxides , 
 with an emphasis on monoperoxyacetals . base - promoted alkylation of hydroperoxides 
 with primary and secondary triflates provided 
 good yields of t - butyl / alkyl peroxides ( 8a11a ) , monoperoxyacetals ( 8c,8b10b , 12b , 13b(24 ) ) , and a 
 2-methoxyethyl peroxide ( 9e ) . tetrahydropyranyl monoperoxyacetals 
 ( 14b , 15b ) were also prepared through acetalization 
 of hydroperoxides with dihydropyran . thermal analysis was conducted on 
 one of the dialkyl peroxides ( 10a ) and one of the monoperoxyacetals 
 ( 10b ) to provide some baseline stability data for each 
 class . the results , detailed in supporting information , revealed that 10a and 10b are relatively 
 stable , undergoing exothermic decomposition only once heated past 
 170 and 120 c , respectively . table 2 illustrates the reactivity of t - butyl / alkyl and trialkylsilyl / alkyl peroxides toward sp organometallics . t - butyl peroxide 8a reacted with an excess of rli over a period of several 
 hours to furnish ethers derived from selective attack on the less 
 hindered oxygen . the corresponding trialkylsilyl 
 peroxide ( 8d ) reacted slowly with n - buli 
 to furnish a large number of products ( tlc ) . from allylsnbu3 and n - buli . reactions with rli proceeded slowly at 78 
 c but were complete within minutes at 0 c . the monoperoxyacetals 
 failed to react with grignard reagents at 78 c but were 
 consumed rapidly at 0 c , providing ethers in yields equal or 
 superior to those obtained with rli . transfer of 1 , 2 , 
 or 3 alkoxides occurred with similar yields ; in each case ; we 
 observed only the products of regioselective displacement of othp . ( a ) rli ( 1.1 equiv ) , 78 
 c ; ( b ) hexylmgbr ( 1.1 equiv ) , 0 c ; ( c ) me3sich2mgcl ( 1.3 equiv ) , 0 c . monoperoxyacetal 8b reacted readily with phli ( 78 c ) and phmgbr ( 0 c ) 
 to furnish good yields of the phenyl ether ( 18a , scheme 2 ) . reaction with 
 an alkenyl magnesium bromide or vinyl lithium , the latter generated 
 in situ , furnished the corresponding enol ethers ; the moderate yields 
 may in part reflect decomposition during purification . reaction of 
 2-thienyl lithium with primary monoperoxyacetals furnished a moderate 
 yield of 2-alkoxythiophenes 18d and 18e , 
 representatives of a class of molecules previously explored only to 
 a limited extent . thf , 
 78 to rt ( rli ) or 
 0 c to rt ( rmgx ) . alkynyllithium or alkynylmagnesium 
 reagents failed to react with a dialkyl peroxide ( 8a ) 
 or a monoperoxyacetal ( 8b ) ; starting materials could 
 be recovered even after prolonged reaction periods ( eq 1).1 neither 
 monoperoxyacetals nor a dialkyl peroxide underwent intermolecular 
 c  o bond formation with enolates ( eq 2 ) or azaenolates ( eq 3 ) ; only slow decomposition 
 was observed . the results were not entirely unexpected given our observations 
 during tandem reactions of enolates with iodoperoxides . in a control experiment , reaction of a thf solution 
 of 8b with stoichiometric potassium t - butoxide ( eq 4 ) resulted in slow formation of byproducts indicative 
 of e1cb fragmentation . the corresponding t - butyl peroxide 8a ( not shown ) decomposed 
 more slowly to furnish citronellal.2 lithiated 1,3-dithianes have been 
 widely applied as acyl anion equivalents for reaction with carbon 
 electrophiles . in the only report of 
 their reactivity toward peroxides , reaction with bistrimethylsilyl 
 peroxide results in preferential transfer of a silyl group . we recently demonstrated successful reaction 
 of thp monoperoxyacetals with lithiated dithianes to furnish s , s , o - orthoesters and 
 derived difluoroalkyl ethers . being curious 
 about the influence of the peroxide electrophile on the reactivity 
 toward inductively stabilized anions , we investigated reactions of 
 a monoperoxyacetal , a silyl / alkyl peroxide , and a dialkyl peroxide 
 toward a common lithiated dithiane ( scheme 3 ) . the monoperoxyacetal 10b and 
 alkyl / silyl peroxide 10d gave similar yields of difluoroether 19 , isolated following fluorodesulfurization of the initial 
 orthoester products . in contrast , the mixed alkyl / t - butyl peroxide 10a was much less reactive . reactions 
 were conducted exclusively in thf ; previous investigations of reactions 
 of lithiated trithianes observed no benefit 
 from the presence of additives ( licl , mgbr2 ) or polar cosolvents ( hmpa ) . trifluoromethyl 
 ethers are of interest as degradation - resistant structural components 
 in agrochemicals and drug molecules . we recently reported an indirect approach to introduction 
 of ocf3 groups via reaction of a monoperoxyacetal with 
 a lithiated trithiane , followed by fluorodesulfurization of the resulting s , s , o - orthocarbonate , and we became interested in a more direct approach 
 based upon reaction of a peroxide with a trifluoromethyl anion . this 
 approach requires the targeted c  o bond formation to occur 
 more rapidly than -elimination of the nucleophile . the trifluoromethyl ether was not observed despite application of 
 different activators , solvents ( dmf , thf ) , or reaction temperatures 
 ( scheme 4 ) . we also 
 failed to detect ether formation for base - promoted reaction with trifluoroacetaldehyde 
 hydrate , or with kcf3 generated 
 via low temperature deprotonation of fluoroform . formation of aldehydes derived from kornblum fragmentation 
 of the peroxide ( see eq 4 ) was observed in some of these reactions . interested in whether the displacements might be more successful in 
 the presence of a lithium cation , we investigated reactions with lithiated 
 trihalomethanes but saw no reaction at temperatures ( 110 c 
 for liccl3 , 50 c for licbr3 ) where 
 the reagents were stable . lithiated 
 ethers ( -alkoxylithiums ) have been employed as synthons for 
 acyl anions and hydroxymethyl anions . as illustrated in table 3 , the alkoxylithium reagent generated from a tributylstannyl 
 mom ether ( 20 ) reacted with primary alkyl / t - butyl peroxides or a monoperoxyacetal to give moderate yields of 
 the mixed o , o - acetals . the 
 same reaction , when repeated with methoxypropyl peroxyacetal 8c , did not proceed to completion . the mixed acetal ( 21d ) was isolated in low yield and accompanied by the tertiary 
 alcohol ( 22 ) derived from trapping of acetone generated 
 from the cleaved acetal ( eq 5).5 we were interested 
 in application of the reaction of monoperoxyacetals and organometallics 
 as an approach to cyclopropyl ethers , a relatively challenging class 
 of targets for which multiple approaches have been reported . in approaching this class of reactions , we were 
 encouraged by the reported reaction of t - butyl perbenzoates 
 with cyclopropyl magnesium bromide . we 
 found that the reaction of monoperoxyacetals with cyclopropyl magnesium 
 bromide furnishes an efficient approach to primary and secondary cyclopropyl 
 alkyl ethers ( table 4 ) . in an effort to gain information 
 about the possible role of single electron transfer in the c o 
 bond - forming step , we investigated reactions of phenylmethylpropyl 
 peroxides ; the derived alkoxy radical undergoes cleavage to acetone 
 and benzyl radical at 10/s ( scheme 5 ) . silyl peroxide 24d was prepared 
 through co(ii)-mediated peroxidation of methallyl benzene with oxygen 
 and triethylsilane . thp acetal 24b was prepared by deprotection of the silyl peroxide and 
 acetalization of the intermediate hydroperoxide . monoperoxyacetal 24b underwent rapid reaction 
 with n - buli to furnish mainly the butyl ether ( 25a ) , accompanied by smaller amounts of the tertiary alcohol 26 and recovered starting material ( table 5 ) . the corresponding reaction with excess 
 hexylmgbr furnished only the hexyl ether ( 25b ) resulting 
 from displacement of othp . in contrast , reaction of di - t - alkyl peroxide 24a with n - buli generated 
 multiple products and only trace amounts of the ether . the reaction 
 of silyl peroxide 24d with n - buli provided 
 the most convincing evidence for the intermediacy of radicals in the 
 form of a significant amount of pentylbenzene product of radical  radical 
 coupling . conditions : n - buli 
 ( 1 equiv ) , thf , 78 c , allow to warm to rt ; hexylmgbr 
 ( 2 equiv ) , 0 c , allow to warm to rt . a competition between a dialkyl 
 peroxide and a monoperoxyacetal 
 for capture of a limiting quantity of n - buli generated 
 only the ether ( 27 ) derived from the monoperoxyacetal 
 ( eq 6).6 a competition 
 between n - buli and phli for a limiting 
 quantity of a monoperoxyacetal revealed a strong preference for reaction 
 with the sp reagent ( eq 7).7 in an effort 
 to probe the basis for the enhanced reactivity of the monoperoxyacetals , 
 we investigated c  o bond formation with 2-methoxyethyl peroxide 9e . this substrate , which possesses the potential for metal 
 chelation but lacks a peroxyacetal , provided the corresponding either 
 in lower yields than had been observed even with simple t - butyl peroxides ( eq 8).8 in an effort to gain better 
 understanding of the reactions described above and the influence of 
 reaction conditions on product formation , we conducted b3lyp/6 - 31+g(d , p ) 
 calculations for the simple model reaction of the transfer of methoxide 
 from a methyl peroxide or peroxyacetal to a methyl anion ( scheme 6 ) . our calculations 
 focused on the impact of changing the metal from li to na and of changing 
 the leaving group from ot - bu to othp . b3lyp/6 - 31+g(d , p ) , 0 k ; units 
 in kcal / mol . thf at 298 
 k with the smd continuum solvent model ; units in kcal / mol and enthalpies 
 in parentheses . all four sets of conditions 
 appear to favor the same mechanism : 
 first , formation of a metal - peroxy complex ( ii ) , second , 
 passage through a four - centered transition state ( ts iii ) , third , formation of a complex of the incipient ether with the 
 metal alkoxide ( iv ) , and , finally , cleavage to final 
 products ( v ) . ( early calculations found the same mechanism 
 for the addition of alkyl lithium reagents to carbon the calculations predict that the lithiated system is significantly 
 more reactive than the sodiated system . this suggests that the metal 
 ion s interaction with the peroxy moiety is primarily electrostatic ; the greater charge density on the smaller li leads to greater stabilization . the presence of the thp group 
 is found to stabilize the initial organometallic - peroxide complex 
 ( ii ) and to dramatically lower the energy for insertion 
 into the peroxide bond . an approximate treatment of thf solvation 
 using the smd continuum model predicts the relative enthalpies of 
 most intermediates and transition states to be several kcal / mol higher 
 in energy than the gas - phase calculations . however , the solvation 
 calculations predict the same trends in reactivity : the li ion and the thp substituent both significantly stabilize both the 
 reactive complex and the transition state for insertion . whereas reactions of dialkyl peroxides are largely limited to transfer 
 of methoxide or primary alkoxide , monoperoxyacetals have significantly enhanced reactivity toward 
 unstabilized carbanions , transferring primary , secondary , or tertiary 
 alkoxides through highly regioselective attack on the nonacetal oxygen 
 of the peroxide . in contrast to peresters , monoperoxyacetals appear 
 to promote alkoxide transfer without significantly destabilizing the 
 peroxide . reaction is observed 
 between monoperoxyacetals and sp and sp rli and rmgx reagents 
 at 78 c ( organolithium reagents ) or 0 c ( grignard 
 reagents ) . both acyclic ( 2-methoxyprop-2-yl ) and cyclic ( thp ) peroxyacetals 
 offer good reactivity ; however , the acyclic peoxyacetals sometime 
 generate side products derived from liberation of a reactive carbonyl 
 group in the presence of the organometallic . the monoperoxyacetals 
 do not undergo intermolecular reactions with enolates or similar stabilized 
 carbanions , paralleling earlier observations from our lab . the monoperoxyacetals also fail to react with 
 metalated alkynes , an interesting outcome given the reported reactivity 
 of lithiated hydroperoxides toward carbanions , as well as our 
 observation of successful reaction of peroxyacetals with inductively 
 stabilized anions such as lithiated dithianes and lithiated ethers . 
 however , the lack of reactivity toward sp carbanions 
 is consistent with results observed with bistrimethylsilyl peroxide , 
 which undergoes mainly silyl exchange with lithiated alkynes . several mechanisms have been discussed 
 with regard to the reaction 
 of dialkyl peroxides with unstabilized organometallics . while early 
 results with unhindered peroxides were consistent with sn2-type attack on the o  o bond , reactions of di - t - alkyl peroxides have been reported 
 to proceed via intermediate alkoxy radicals . our work found no evidence for radical intermediates in attack of 
 organolithium reagents on thp peroxyacetals . if the reactions 
 involve neither simple displacement nor cleavage 
 to alkoxy radicals , then what ? lithiated peroxides are often thought 
 to react with nucleophiles through oxenoid - type insertion into the 
 c  li bond ; attack on alkenyl lithium and cyclopropyl lithium 
 appears to occur without loss of stereochemistry . however , whereas the transfer of lio from lithiated hydroperoxides 
 to organolithium reagents has been calculated to involve in - line arrangement 
 of the carbanion , the lithiated oxygen , and the departing oxygen , our calculations suggest side - on insertion 
 of the rli into the lewis acid activated o  o bond . this theoretical 
 result is supported by the similar yields obtained for transfer of 
 primary , secondary , and tertiary alkoxides , a result which would seem 
 to rule out an sn2-type attack on the backside of the breaking 
 o  o bond . calculations predict , and experiments confirm , that 
 the presence of the acetal group significantly lowers the energy for 
 insertion of unstabilized organometallics and directs the reaction 
 toward exclusive transfer of the nonanomeric oxygen . the bidentate 
 coordination available to the organometallic / lewis acid is not sufficient 
 to explain the results , as evidenced by the poor reactivity of the 
 methoxyethyl peroxide . however , the interaction of lewis acids with 
 peroxyacetals and ozonides ( 1,2,4-trioxolanes ) has been previously 
 demonstrated to activate both c  o and o  o bonds . in conclusion , we have shown that monoperoxyacetals , 
 readily prepared 
 and easily handled derivatives of hydroperoxides , enable highly efficient 
 intermolecular transfer of alkoxide to unstabilized organolithium 
 and organomagnesium reagents along with some inductively stabilized 
 organolithium species . the peroxyacetal activating group promotes 
 highly selective transfer of the nonanomeric or , regardless of steric 
 bulk . the bond - forming process , which appears to involve metal - promoted 
 insertion into the o o linkage , appears to be mechanistically 
 distinct from similar reactions of alkyl or alkyl silyl peroxides . the new methodology offers a new tool with which to approach ethers , 
 including some poorly accessible through existing methods . reagents and solvents were used as supplied commercially , except 
 for dcm and thf , which were distilled from cah2 and na / ph2co , respectively . thin - layer 
 chromatography ( tlc ) was performed on 0.25 mm hard - layer silica g 
 plates visualized with a uv lamp or by staining : 1% ceric sulfate 
 and 10% ammonium molybdate in 10% h2so4 ( general 
 stain , after heating ) ; 3% vanillin in 3% h2so4 in etoh ( general stain , after heating ) ; or a 1% n , n-dimethyl - p - phenylenediamine 
 in 1:20:100 acetic acid / water / methanol ( specific for peroxides ) . unless otherwise noted , nmr spectra were acquired 
 in cdcl3 ; h spectra are reported as chemical 
 shift ( multiplicity , j couplings in hz , number of 
 protons ) . ir spectra were recorded as neat films on a zrse crystal ; 
 selected absorbances are reported in cm . abbreviations : 
 hexane = hex ; ea = ethyl acetate ; thf = tetrahydrofuran ; tbdms ( or 
 tbs ) = tert - butyldimethylsilyl ; thp = tetrahydropyranyl . optimized geometries , harmonic vibrational 
 frequencies , and electronic energies of all structures in scheme 6 were obtained with 
 the b3lyp level of density functional theory and the 6 - 31+g(d , p ) basis 
 set . all minima reported ( structures i , ii , iv , and v ) contain all 
 real frequencies , and all transition states ( structures ts iii ) contain one imaginary frequency . intrinsic reaction coordinate 
 calculations confirmed that each transition state connected a metal - peroxy 
 complex ii and the corresponding metal alkoxide - ether 
 complex iv . the relative electronic energies were corrected 
 by the differences in zero - point vibrational energy scaled by 0.9806 . solution - phase enthalpies were determined as 
 follows : the thermal corrections to the electronic energies were calculated 
 based on the b3lyp/6 - 31+g(d , p ) geometries and harmonic frequencies . solvation corrections were based on single - point energy calculations 
 using the continuum smd model of truhlar and co - workers . [ 75 - 91 - 2 ] , 5.5 m in decane , was used as purchased . [ 4676 - 84 - 0 ] was synthesized using a modified version of a known procedure . to a 0 c solution of 50 wt % aq . h2so4 ( 0.1 ml ) the mixture was stirred for 10 
 min , after which 3,4-dihydro-2h - pyran ( 4.94 g , 58.8 
 mmol ) was added over a period of 3 min . the reaction was stirred for 
 1 h at 0 c and then diluted with sat . the solution was extracted with ether ( 150 ml ) , and the organic 
 layer was washed with aq . sat . the residue obtained 
 was purified by silica gel flash chromatography using a gradient of 
 425% ea / hex to afford the hydroperoxide as a thick and colorless 
 oil ( 4.60 g , 66% ) . [ 10027 - 74 - 4 ] 
 was prepared as a colorless oil ( 82% , 878 mg ) from 2,3-dimethyl-2-butene 
 ( 10.0 mmol , 841 mg ) using a known procedure.rf = 0.3 ( 15% ea : hex ) . [ 123369 - 58 - 4 ] was prepared by alkylation 
 of a 1,1-dihydroperoxycyclodecane , 
 followed by hydrolysis of the resulting bisperoxyacetal . a solution of 3,7-dimethyloct-6-en-1-ol 
 ( 0.936 g , 
 6 mmol ) in dry dcm ( 18 ml ) was cooled to 0 c , and triflic 
 anhydride ( 1.4 equiv ) and 2,6-lutidine ( 1.5 equiv ) were sequentially 
 added via syringe . the reaction was stirred for 15 min at 0 c 
 and then diluted with ice - cold hexane ( 40 ml ) . khso4 ( 40 ml ) , 
 and the separated aqueous layer was extracted with another portion 
 of cold hex ( 25 ml ) . the combined organic layers were dried over na2so4 and concentrated on a rotary evaporator ( bath 
 temperature 10 c ) . the residue was subjected to 0.5 mmhg for 
 approximately 5 min to generate nearly pure 3,7-dimethyloct-6-en-1-yl 
 trifluoromethanesulfonate ( 1.693 g , 98% ) as a light brown oil , which 
 was placed in a 20 c freezer and used within an hour : rf = 0.59 ( 10% ea / hex ) ; h nmr : 5.115.07 ( m , 1h ) , 4.614.57 ( m , 2h ) , 
 2.061.96 ( m , 2h ) , 1.931.85 ( m , 1h ) , 1.721.68 
 ( m , 1h ) , 1.70 ( s , 3h ) , 1.661.64 ( m , 1h ) , 1.62 ( s , 3h ) , 1.421.32 
 ( m , 1h ) , 1.291.20 ( m , 1h ) , 0.96 ( d , j = 6.3 
 hz , 3h ) ; c nmr : 131.8 , 123.9 , 118.5 ( q , j = 323 hz ) , 76.2 , 36.6 , 36.0 , 28.6 , 25.6 , 25.1 , 19.0 , 17.6 . to a 0 c solution of cyclododecanone-1,1-dihydroperoxide 
 ( 2.196 g , 9.469 mmol , synthesized as previously described ) in dry thf ( 50 ml ) was added kotbu ( 2 equiv ) , followed by the triflate described above ( 6.0 g , 20.8 
 mmol ) . the reaction mixture was stirred until the starting material 
 was no longer visible ( tlc , 20 min ) . the reaction mixture 
 was then quenched with water ( 25 ml ) and extracted with ea ( 50 ml 
  2 ) . the residue 
 was purified by silica chromatography using 1% ea / hex to furnish 1,1-bis-(3,7 
 dimethyl-6-octenylperoxy ) cyclododecane ( 2.84 g , 59% ) as a colorless 
 oil : rf = 0.75 ( 10% ea : hex ) ; h nmr : 5.10 ( m , 2h ) , 4.173.99 ( m , 4h ) , 2.071.91 ( m , 
 4h ) , 1.721.64 ( m , 9h ) , 1.69 ( s , 3h ) , 1.61 ( s , 3h ) , 1.581.53 
 ( m , 7h ) , 1.481.28 ( m , 20h ) , 1.241.15 ( m , 2h ) , 0.92 
 ( d , j = 6.5 , 6h ) ; c nmr : 131.2 , 124.6 , 
 113.1 , 73.4 , 37.1 , 34.6 , 29.7 , 27.0 , 26.1 , 25.7 , 25.4 , 22.3 , 21.9 , 
 19.6 , 19.4 , 17.6 ; hrms ( tofms - es ) : calcd for c32h60o4na ( m + na ) 531.4389 found : 531.4373 ; ir : 
 2926 , 2850 , 1445 , 1052 . to a room temperature solution of the 
 bisperoxyacetal ( 1.01 g , 
 2 mmol ) in thf ( 20 ml ) was added a solution of 50% aq . h2so4 ( 1.8 mmol , 6 equiv ) , and the reaction mixture was 
 stirred at 55 c until starting material was nearly consumed 
 ( tlc , 13 h ) . na2co3 ( 25 ml ) , and the resulting mixture 
 was extracted with ea ( 30 ml  2 ) . the combined organic layers 
 were dried over na2so4 and concentrated on a 
 rotary evaporator . the crude product was purified by silica chromatography 
 using 13% ea / hex to furnish hydroperoxide 4 as 
 a colorless oil ( 0.364 mg , 53% ) . the molecule has previously been 
 reported without characterization : rf = 0.4 ( 10% ea / hex ) ; h nmr : 8.53 
 ( s , 1h ) , 5.09 ( m , 1h ) , 4.104.00 ( m , 2h ) , 2.061.93 
 ( m , 2h ) , 1.731.63 ( m , 1h ) , 1.68 ( s , 3h ) , 1.60 ( s , 3h ) , 1.541.35 
 ( m , 2h ) , 1.331.14 ( m , 2h ) , 0.91 ( d , j = 6.5 , 
 3h ) ; c nmr : 131.3 , 124.6 , 75.5 , 37.1 , 34.3 , 29.5 , 25.7 , 
 25.4 , 19.5 , 17.6 . ir : 36173101 ( broad peak ) , 2915 , 1455 , 1377 , 
 1053 ( mass spec not attempted due to volatility ) . [ 4952 - 03 - 8 ] was prepared through a two - step 
 procedure . ( cas 
 634600 - 89 - 8 ) was prepared through a modification of a reported procedure . 1-methyl cyclohexene ( 0.96 g , 10 mmol ) and et3sih ( 2.32 g. , 20 mmol ) were sequentially added to a solution 
 of co(acac)2 ( 1 mmol ) in ethanol ( 35 ml ) . the reaction 
 mixture was placed under an atmosphere of o2 ( balloon ) 
 until no starting material was observed ( tlc , 14 h ) . the residue 
 obtained upon concentration in vacuo was purified by silica gel chromatography 
 using 18% ea : hex to furnish the 1-methyl-1-cyclohexyl triethylsilyl 
 peroxide as a as colorless oil ( 0.844 g , 34% ) : rf = 0.7 ( 10% ea / hex ) . to a solution of the triethylsilylperoxide 
 ( 0.78 g , 3.19 mmol ) in thf ( 10 ml ) was added tetra n - butyl ammonium fluoride ( 1 m solution in thf , 1.2 equiv ) . the reaction was stirred at room temperature until no starting material 
 could be observed ( tlc , 5 min ) . the residue obtained upon 
 concentration in vacuo was diluted with hexane ( 30 ml ) and washed 
 with water ( 10 ml ) . the residue was purified 
 by short - column ( 3 ) flash chromatography with 5% ea / hex ( two 
 iterations were required to remove silanol / siloxane byproducts ) to 
 furnish the hydroperoxide 5 as a colorless oil ( 0.266 
 g , 64% ) . although the hydroperoxide is commercially available , nmr 
 data are difficult to access and are provided here for convenience : rf = 0.4 ( 10% ea : hex ) ; h nmr : 7.34 
 ( s , 1h ) , 1.801.74 ( m , 2h ) , 1.631.53 ( m , 2h ) , 1.511.38 
 ( m , 5h ) , 1.341.29 ( m , 1h ) , 1.25 ( s , 3h ) ; c nmr : 
 81.7 , 34.4 , 25.6 , 23.8 , 22.2 , 6.55 , 5.76 . [ 60956 - 33 - 4 ] 
 was prepared using a route analogous to that employed for hydroperoxide 4 . 3-phenylpropyl trifluoromethanesulfonate [ 66950 - 73 - 0 ] 
 was prepared ( 1.34 g , quant . ) as a light brown oil from 3-phenylpropanol 
 ( 0.681 g , 5 mmol ) using the procedure described above : rf = 0.5 ( 10% ea / hex ) . other spectral data matched 
 those in a previous report . using 
 a similar procedure as described earlier , cyclododecanone 
 1,1-dihydroperoxide ( 1.05 g , 4.545 mmol ) was reacted with the 3-phenylpropyl 
 triflate ( 2.6 g , 10 mmol ) to furnish the bisperoxyacetal ( 1.4381 g , 
 67% ) as a colorless oil : rf = 0.6 ( 15% 
 ea / hex ) ; h nmr : 7.327.29 ( m , 4h ) , 7.237.21 
 ( m , 6h ) , 4.11 ( t , j = 6.4 , 4h ) , 2.73 ( t , j = 7.5 , 4h ) , 2.021.95 ( m , 4h ) , 1.741.70 
 ( m , 4h ) , 1.561.46 ( m , 4h ) , 1.451.31 ( m , 14h ) ; c nmr : 141.7 , 128.4 , 128.3 , 125.8 , 113.3 , 74.2 , 32.3 , 29.5 , 
 27.1 , 26.1 , 22.3 , 22.0 , 19.4 ; ir : 2914 , 2845 , 1462 , 1053 hydrolysis 
 of the bisperoxyacetal ( 1.35 g , 2.88 mmol ) by a similar 
 procedure as described above furnished hydroperoxide 6 as a colorless oil ( 0.725 g , 82% ) : rf = 0.57 ( 20% ea / hex ) . the 
 title compound was prepared by an analogous strategy as described 
 for hydroperoxides 4 and 6 . 10-phenyldecyl 
 trifluoromethanesulfonate ( 1.098 g , quant . ) was prepared from 10-phenyldecanol 
 ( 0.70 g , 3 mmol ) as a light brown oil : rf = 0.65 ( 10% ea / hex ) ; h nmr : 7.337.28 ( m , 2h ) , 
 7.227.18 ( m , 3h ) , 4.56 ( t , j = 6.5 hz , 2h ) , 
 2.63 ( t , j = 7.7 hz , 2h ) , 1.85 ( m , 2h ) , 1.691.59 
 ( m , 2h ) , 1.461.33 ( m , 12h ) ; c nmr : 142 , 128.4 , 
 128.2 , 125.5 , 118.6 ( q , j = 320 hz ) , 77.7 , 35.9 , 
 31.5 , 29.4 , 29.37 , 29.30 , 29.27 , 29.22 , 28.8 , 25.0 . hrms ( esi ) : calcd 
 for c17h25f3nao3 s ( m 
 + na ) 389.1374 , found 389.1369 . using a similar procedure as 
 described above , reaction of 1,1-dihydroperoxycyclododecanone ( 0.293 g , 1.26 mmol ) and the 10-phenyl decyl triflate ( 1.02 g , 2.787 
 mmol ) was used to prepare 1,1-bis-(10-phenyldecyldioxy)cyclodecanone : 
 ( 0.834 g , 99% ) as a colorless oil : rf = 
 0.74 ( 15% ea / hex ) ; h nmr : 
 7.327.29 ( m , 4h ) , 7.217.19 ( m , 6h ) , 4.09 ( t , j = 6.6 , 4h ) , 2.62 ( t , j = 7.7 , 4h ) , 1.721.59 
 ( m , 12h ) , 1.371.30 ( m , 42h ) ; c nmr : 142.9 , 128.4 , 
 128.2 , 125.5 , 113.1 , 75.0 , 36.0 , 31.5 , 29.57 , 29.53 , 29.48 , 29.36 , 
 27.8 , 27.0 , 26.2 , 26.1 , 22.3 , 21.9 , 19.4 . hrms ( tof - ms - es+ ) : calcd 
 for c44h72o4na ( m + na ) 687.5328 found 687.5300 ; ir : 2914 , 2845 , 1462 , 1053 . using 
 a procedure similar to that described above , hydrolysis of 
 the bis-(10-phenyldecyl)peroxyacetal ( 0.755 g , 1.14 mmol ) furnished 
 10-phenyldecyl hydroperoxide as a colorless oil ( 0.243 g , 64% ) : rf = 0.55 ( 15% ea / hex ) ; h nmr : 8.04 ( t , j = 6.5 , 1h ) , 7.337.28 ( m , 2h ) , 7.227.20 ( m , 3h ) , 
 4.04 ( t , j = 6.6 , 2h ) , 2.63 ( t , j = 7.7 , 2h ) , 1.681.61 ( m , 4h ) , 1.32 ( m , 12h ) ; c nmr : 142.9 , 128.4 , 128.2 , 125.5 , 76.6 , 36.0 , 31.5 , 29.5 , 29.4 , 
 29.3 , 27.5 , 25.9 ; hrms ( tof - ms - ei+ ) : calcd for c16h25o ( m  oh ) 233.1905 ; found : 233.1920 ; 
 ir : 3390 , 2922 , 2852 , 1453 , 696 the hydroperoxide ( 10 mmol in a minimum amount of thf ) 
 was added under nitrogen to a 0 c solution of kotbu ( 10 mmol ) in dry thf ( 50 ml ) . the reaction mixture was stirred 
 for 3 min , after which was added preformed alkyl triflate ( 10 mmol , 
 neat from syringe , remaining triflate rinsed into the reaction using 
 1 ml of thf ) . the reaction was stirred for 15 min at the same temperature 
 and then quenched with water ( 20 ml ) . the mixture was extracted with 
 10% ea / hex ( 50 ml  2 ) , and the organic layer was dried over 
 na2so4 . the residue obtained upon concentration 
 was purified by flash silica chromatography using 1% ea / hex . acetalization 
 of alkyl hydroperoxides to form tetrahydropyranyl ( thp ) monoperoxyacetals 
 employed a modification of a reported procedure . a mixture of alkyl hydroperoxide ( 1.0 mmol ) and 2,3-dihydropyran 
 ( 1.0 mmol ) was cooled to 0 c , after which was added 0.05 ml 
 of a solution of 10% h2so4 in thf . the stirred 
 reaction mixture was allowed to warm to rt over a period of 45 min . the reaction was diluted with 10% ether / hex ( 15 ml ) , and the resulting 
 solution was washed with water ( 2 ml ) . the separated organic layer 
 was dried over na2so4 and concentrated under 
 reduced pressure . dialkyl peroxide 
 synthesis using silver oxide was based upon a modification of reported 
 procedures . the alkyl hydroperoxide ( 1.0 
 mmol ) was added to a suspension ( ea , 10 ml ) of freshly prepared silver 
 oxide ( 1.2 mmol ) . alkyl halide ( 1.0 mmol ) was added , and the reaction 
 was stirred at rt until no starting material could be observed ( tlc , 
 approximately 410 h ) . the reaction mixture was filtered through 
 a small pad of celite , and the residue was washed with ea ( 1020 
 ml ) . the combined filtrates were concentrated , and the residue was 
 purified by silica gel chromatography using 13% ea / hex . trialkylsilylation 
 was performed based upon a reported procedure , except for a different 
 order of addition and the use of water rather than aqueous acid for 
 the wash . to a room temperature solution 
 of alkyl hydroperoxide ( 1.0 mmol ) in dmf ( 2 ml ) was added tert - butyl dimethylsilyl chloride ( 1.2 mmol ) , followed by 
 imidazole ( 1.4 mmol ) . the reaction was stirred for 1 h and then diluted 
 with water ( 10 ml ) . the hexane extracts ( 1  50 , 1  10 
 ml ) were dried over na2so4 and concentrated 
 under reduced pressure . [ 1592933 - 34 - 0 ] : using method 
 a ( above ) , t - butyl hydroperoxide ( 5.5 m in decane , 
 0.588 ml , 3.24 mmol ) was reacted with 3,7-dimethyl-6-octenyl triflate 
 ( described above in relation to preparation of peroxide 4 , 1.025 g , 3.559 mmol ) to furnish 8a as a colorless 
 oil ( 0.511 g , 69% ) ; rf = 0.6 ( 10% ea / hex ) . spectral data matched those in literature reports . using method a , thp hydroperoxide 1 ( 0.63 g , 5.34 mmol ) was reacted with 3,7-dimethyl-6-octenyl 
 triflate ( 1.69 g , 5.87 mmol ) to furnish peroxide 9a as 
 a colorless oil ( 0.854 g , yield : 62% ) rf = 0.42 ( 10% ea / hex ) ; h nmr : 5.15 ( t , j = 3.5 hz , 1h ) , 5.10 ( m , 1h ) , 4.194.00 ( m , 2h ) , 4.02 ( m , 
 1h ) , 3.663.61 ( m , 1h ) , 1.98 ( m , 2h ) , 1.781.71 ( m , 
 2h ) , 1.701.65 ( m , 1h ) , 1.68 ( s , 3h ) , 1.641.53 ( m , 
 5h ) , 1.60 ( s , 3h ) , 1.491.42 ( m , 1h ) , 1.411.32 ( m , 
 1h ) , 1.231.1 ( m , 1h ) , 0.92 ( d , j = 6.6 hz , 
 3h ) ; c nmr :  : 131.2 , 124.7 , 100.8 , 73.7 , 62.5 , 
 37.1 , 34.6 , 29.6 , 27.96 , 25.7 , 25.4 , 25.1 , 19.7 , 19.5 , 17.6 . hrms 
 ( esi tof ) calcd for c15h28nao3 ( m + na ) : 279.1931 ; found : 279.1934 ; ir : 2923 , 2861 , 1440 , 
 1040 . using method a , hydroperoxide 3 ( 0.674 g , 6.35 mmol , 1.5 equiv ) was reacted with 3,7-dimethyl-6-octenyl 
 triflate ( 1.21 g , 4.2 mmol ) to furnish 8c as a colorless 
 oil ( 0.627 g , yield : 61% ) ; rf = 0.4 ( 10% 
 ea / hex ) ; h nmr : 5.1 ( m , 1h ) , 4.114.01 ( m , 2h ) , 
 3.33 ( s , 3h ) , 2.061.91 ( m , 2h ) , 1.711.64 ( m , 1h ) , 
 1.69 ( s , 3h ) , 1.61 ( s , 3h ) , 1.621.54 ( m , 1h ) , 1.471.31 
 ( m , 2h ) , 1.40 ( s , 6h ) , 1.241.10 ( m , 1h ) , 0.91 ( d , j = 6.5 hz , 3h ) ; c nmr131.2 , 124.7 , 104.5 , 
 73.4 , 49.2 , 37.1 , 34.6 , 29.6 , 25.7 , 25.4 , 22.76 , 22.74 , 19.5 , 17.6 ; 
 hrms ( tof - ms - es+ ) calcd for c14h28nao3 ( m + na ) : 267.1931 ; found : 267.1926 ; ir : 2954 , 2874 , 1457 , 836 . using method d , alkyl hydroperoxide 4 ( 0.22 g , 1.279 mmol ) was silylated with t - butyldimethylsilyl chloride ( tbs - cl ) to furnish 8d as 
 a colorless oil ( 0.212 g , 58% ) : rf = 0.75 
 ( 10% ea / hex ) ; h nmr : 5.12 ( m , 1h ) , 4.063.97 ( 2h ) , 
 2.061.91 ( m , 2h ) , 1.69 ( s , 3h ) , 1.671.59 ( m , 1h ) , 
 1.61 ( s , 3h ) , 1.591.51 ( m , 1h ) , 1.461.30 ( m , 2h ) , 
 1.221.15 ( m , 1h ) , 0.95 ( s , 9h ) , 0.91 ( d , j = 6.6 ) , 0.17 ( s , 6h ) ; c nmr : 131.2 , 124.6 , 75.3 , 37.1 , 
 34.5 , 29.6 , 26.1 , 25.7 , 25.4 , 19.6 , 18.1 , 17.6 , 5.9 ; hrms 
 ( tof - ms - ei+ ) calcd for c16h34nao2si ( m + na ) : 309.2220 ; found : 309.2218 ; ir : 2928 , 2857 , 1461 , 834 . [ 419568 - 76 - 6 ] : using method a , tert - butyl 
 hydroperoxide ( 1.8 ml , 5.06.0 m in decane , 10 mmol ) was reacted 
 with 3-phenyl propyl triflate ( 2.68 g , 10 mmol ) to furnish 9a as a colorless liquid ( 1.5151 g. 73% ) . [ 1630792 - 49 - 2 ] : using 
 method a , 
 thp hydroperoxide 1 ( 1.18 g , 10 mmol ) was reacted with 
 3-phenylpropyl triflate ( 2.68 g , 10 mmol ) to furnish peroxide 9b as a colorless oil ( 1.937 g , 82% ) ; rf = 0.66 ( 15% ea / hex ) . 2-methoxyethyl 
 trifluoromethanesulfonate [ 112981 - 50 - 7 ] was prepared ( 2.08 g , quant ) 
 from 2-methoxyethanol ( 760 mg , 10.0 mmol ) using the procedure described 
 above and used without purification . spectral data matched those reported.rf = 0.5 ( 30% ea / hex ) . using method a , alkyl hydroperoxide 6 ( 0.70 g , 4.6 
 mmol ) was reacted with 2-methoxyethyl trifluoromethanesulfonate ( 0.956 
 g , 4.6 mmol ) to furnish 9e as a colorless oil ( 0.723 
 g , 74% ) : rf = 0.62 ( 20% ea / hex ) ; h nmr : 7.327.27 ( 2h ) , 7.227.18 ( 3h ) , 4.15 
 ( m , 2h ) , 4.05 ( t , j = 6.4 , 2h ) , 3.62 ( m , 2h ) , 3.40 
 ( s , 3h ) , 2.71 ( t , j = 7.8 , 2h ) , 2.011.93 
 ( 2h ) ; c nmr : 141.6 , 128.46 , 128.39 , 125.9 , 73.59 , 73.54 , 
 69.8 , 59.1 , 32.2 , 29.4 ; hrms ( tof - ms - ci+ ) calcd for c12h18o3na [ m + na ] : 233.1154 ; found : 
 233.1152 ; ir : 2924 , 1496 , 1453 , 745 . using method 
 a , t - butyl hydroperoxide 
 ( 1.41 ml , 5.06.0 m in decane , 7.76 mmol ) was reacted with 
 10-phenyldecyl triflate ( 3.125 g , 8.54 mmol ) to furnish 10a as a colorless oil ( 2.42 g , 92% ) . rf = 0.73 ( 10% ea / hex ) ; h nmr : 7.337.20 ( m , 2h ) , 
 7.227.17 ( m , 3h ) , 3.96 ( t , j = 6.7 hz , 2h ) , 
 2.62 ( t , j = 7.8 hz , 2h ) , 1.691.56 ( m , 4h ) , 
 1.321.28 ( m , 12h ) , 1.27 ( s , 9h ) ; c nmr :  : 
 142.9 , 128.4 , 128.2 , 125.5 , 80.0 , 75.1 , 36.0 , 31.5 , 29.5 , 29.3 , 27.8 , 
 26.3 , 26.2 . hrms ( esi tof ) : calcd for c20h34nao2 ( m + na ) : 329.2451 ; found : 329.2470 ; ir : 
 2924.8 , 2853.72 , 1361.5 , 697 . [ 1630792 - 52 - 7 ] : using 
 method a , 
 thp hydroperoxide 2 ( 0.20 g , 1.77 mmol ) was reacted with 
 10-phenyldecyl triflate ( 0.65 g , 1.775 mmol ) to furnish 10b as a colorless oil ( 0.448 g , 75% ) ; rf = 0.42 ( 10% ea / hex ) . spectral properties matched those in a literature 
 report . using method d , alkyl hydroperoxide 7 ( 0.22 g , 0.89 mmol ) was converted into the corresponding 
 silyl peroxide 10d , which was obtained as a colorless 
 oil ( 0.267 g , 82% ) : rf = 0.8 ( 10% ea / hex ) ; h nmr : 7.327.28 ( m , 2h ) , 7.227.19 ( m , 3h ) , 
 3.99 ( t , j = 6.6 hz , 2h ) , 2.63 ( t , j = 7.7 hz , 2h ) , 1.661.56 ( m , 4h ) , 1.32 ( m , 12h ) , 0.97 ( s , 
 9h ) , 0.19 ( s , 6h ) ; c nmr : 142.9 , 128.4 , 128.2 , 125.5 , 
 76.6 , 36.0 , 31.5 , 29.5 , 29.3 , 27.7 , 26.2 , 26.1 , 18.1 , 5.8 ; 
 hrms ( esi tof ) calcd for c22h40nao2si ( m + na ) : 387.2690 ; found : 387.2677 ; ir : 2925 , 2854 , 1462 , 
 1248 . [ 38375 - 34 - 7 ] : 1-octyl trifluoromethanesulfonate [ 71091 - 89 - 9 ] was 
 prepared ( 3.08 g , 98% ) as a light brown oil from 1-octanol ( 1.56 g , 
 12 mmol ) using the general procedure described above . the h nmr spectrum matched data previously reported : rf = 0.52 ( 10% ea / hex ) ; h nmr : 4.55 ( t , j = 6.54 , 2h ) , 1.84 ( m , 2h ) , 
 1.461.40 ( m , 2h ) , 1.361.29 ( m , 8h ) , 0.90 ( t , j = 6.9 , 3h ) ; c nmr : 118.2 ( q , j = 320.1 hz ) , 76.7 , 31.6 , 29.2 , 28.9 , 28.8 , 25.0 , 22.5 , 14.0 . t - butyl hydroperoxide ( 1.81 ml , 5.5 m in decane , 
 10 mmol ) was reacted with octyl triflate ( 2.88 g , 11 mmol ) to furnish 11a as a colorless oil ( 1.78 g , 88% ) : rf = 0.79 ( 10% ea / hex ) . the molecule has been previously reported 
 without spectral characterization : h nmr : 3.93 ( t , j = 6.7 hz , 2h ) , 1.631.55 
 ( m , 2h ) , 1.341.26 ( m , 10h ) , 1.25 ( s , 9h ) , 0.88 ( t , j = 6.9 hz , 3h ) ; c nmr : 79.9 , 75.1 , 31.8 , 29.4 , 
 29.2 , 27.8 , 26.3 , 26.2 , 22.6 , 14.0 ; hrms ( esi - tof - ms ) calcd for c12h26nao2 ( m + na ) : 225.1825 ; found : 
 225.1840 ; ir : 2924 , 2856 , 1361 , 1197 . [ 1630792 - 51 - 6 ] : decyl 
 trifluoromethanesulfonate 
 [ 53059 - 89 - 5 ] was prepared ( 3.1 g , quant = 2.9 g ) as a light brown 
 oil from 1-decanol ( 1.58 g , 10.0 mmol ) using the procedure described 
 above . spectra closely matched those in previous reports : rf = 0.52 ( 10% ea / hex ) ; h nmr : 4.55 ( t , j = 6.5 hz , 2h ) , 1.84 ( m , 
 2h ) , 1.43 ( m , 2h ) , 1.361.28 ( m , 12h ) , 0.9 ( t , j = 6.8 hz , 3h ) ; c nmr : 118.6 ( q , jc  f = 320 hz ) , 77.7 , 31.8 , 29.4 , 29.3 , 
 29.2 , 28.8 , 25.0 , 22.6 , 14.0 . using method a , 2-tetrahydropyranyl 
 hydroperoxide 2 ( 1.18 g , 10 mmol ) was reacted with decyl 
 triflate ( 2.98 g , 10 mmol ) to furnish peroxide 12b as 
 a colorless oil ( 2.05 g , 79% ) ; rf = 0.56 
 ( 15% ea / hex ) . [ 1630792 - 50 - 5 ] : 2-octyl trifluoromethanesulfonate 
 [ 58864 - 30 - 5 ] was prepared ( 3.58 g , estimated 91% ) as a light brown 
 oil from 2-octanol ( 2.0 g , 15 mmol ) using the procedure described 
 above . rf = 0.3 ( 10% ea / hex ) . , hydroperoxide 2 ( 0.595 
 g , 5.01 mmol ) was reacted with 2-octyl triflate ( 1.47 g , 5.61 mmol ) 
 to furnish 13b as a colorless oil ( 0.808 g , 70% ) rf = 0.61 ( 20% ea / hex ) . [ 685877 - 38 - 7 ] : 
 using method b , acetalization 
 of 2-tetrahydropyranyl hydroperoxide 2 ( 0.35 g , 2.97 
 mmol ) with dihydropyran ( 0.249 g , 2.97 mmol ) furnished peroxide 14b as a colorless oil ( 0.493 g , 84% ) . this molecule has been 
 previously prepared without nmr characterization : rf = 0.50 ( 10% ea / hex ) ; h nmr : 5.22 ( m , 2h ) , 4.09 ( m , 1h ) , 4.00 ( m , 1h ) , 3.633.60 
 ( m , 2h ) , 1.761.74 ( m , 4h ) , 1.661.53 ( m , 8h ) ; c nmr : 101.8 , 100.2 , 62.5 , 62,1 , 27.9 , 27.7 , 25.1 , 25.0 , 
 19.6 , 19.4 . using method b , hydroperoxide 5 ( 0.266 g , 2.04 mmol ) was reacted with dihydropyran ( 0.171 
 g , 2.04 mmol ) to furnish 15b as a colorless oil ( 0.326 
 g , 74% ) . rf = 0.50 ( 10% ea / hex ) ; h nmr : 5.04 ( broad triplet , 1h ) , 4.02 ( m , 1h ) , 3.60 ( m , 1h ) , 
 1.75 ( m , 5h ) , 1.681.53 ( m , 6h ) , 1.471.35 ( m , 6h ) , 
 1.26 ( s , 3h ) ; c nmr : 101.0 , 81.5 , 62.7 , 35.0 , 27.8 , 25.7 , 
 25.1 , 24.3 , 22.5 , 22.3 , 20.0 ; hrms ( esi tof ) calcd for 
 c12h22nao3 ( m + na ) : 237.1461 ; found : 
 237.1469 ; ir : 2931 , 2852 , 1443 , 962 . using a known procedure , cross - metathesis of 1-octene ( 6.72 g , 4.8 mmol ) 
 and allyl bromide ( 1.45 g , 12 mmol ) in the presence of the grubbs 
 ii catalyst furnished 1-bromo-2-undecene ( 1.109 g , 80% ) as a colorless 
 oil consisting of a 84:16 e / z mixture 
 using a known procedure . the portions of the spectra corresponding 
 to the major ( e ) isomer closely matched a previous report [ 67952 - 61 - 8]:rf = 0.8 ( hexane ) ; h nmr : ( both isomers , 
 partial integrals given ) : 5.825.58 ( m , 2h ) , 4.01 ( d , j = 8.3 hz , 0.32 h ) , 3.96 ( d , j = 8.2 hz , 
 1.68 h ) , 2.14 ( m , 0.32h ) , 2.07 ( m , 1.68 ) , 1.401.35 ( m , 2h ) , 
 1.341.28 ( m , 10h),5.82 0.89 ( t , j = 6.8 hz , 3h ) ; c nmr : ( major isomer ) : 136.7 , 126.2 , 33,6 , 
 32.0 , 31.9 , 29.4 , 29.2 , 29.1 , 28.8 , 22.7 , 14.1 . using method 
 c , hydroperoxide 2 ( 0.118 mg , 1 mmol ) was reacted with 
 an e / z - mixture of 2-undecenyl bromide 
 ( 0.232 g , 1.0 mmol ) to furnish peroxide 16b as a colorless 
 oil ( 0.197 mg , 73% ) consisting of an inseparable 84:16 e / z mixture : rf = 0.42 
 ( 10% ea / hex ) ; h nmr : 5.825.74 ( m , 1h ) , 5.695.55 
 ( m , 1h ) , 5.16 ( m , 1h ) , 5.64 ( d , j = 6.8 hz , 0.24 
 h ) , 4.51 ( d , j = 6.8 hz , 1.76 h ) , 4.01 ( m , 1h ) , 3.643.60 
 ( m , 1h ) , 2.132.02 ( m , 2h ) , 1.731.68 ( m , 2h ) , 1.651.53 
 ( m , 4h ) , 1.381.35 ( m , 2h ) , 1.311.26 ( m , 10h ) , 0.87 
 ( t , j = 6.8 hz , 3h ) ; c nmr : 137.8 , 123.7 , 
 100.8 , 76.2 , 62.4 , 32.3 , 31.8 , 29.4 , 29.2 , 29.1 , 28.8 , 27.8 , 25.1 , 
 22.6 , 19.6 , 14.0 . hrms ( tof - ms - es+ ) calcd for c16h30nao3 ( m + na ) : 293.2087 ; found : 293.2087 ; ir : 
 2923 , 2851 , 1202 , 962 . the alkyllithium ( 0.55 mmol , 
 1.1 equiv , typically as 
 a solution in hex ) was added to the solution of peroxide ( 0.50 mmol ) 
 in dry thf ( 3 ml ) at 78 c , and the reaction was stirred 
 for 15 min . for thp monoperoxyacetals , the reaction was brought to 
 room temperature for 15 min and then quenched with water ( 2 ml ) ; for 
 other peroxides , the reaction was allowed to stir at room temperature 
 for the time indicated . the mixture was extracted with 20% ether in 
 hex ( 1  25 , 1  5 ml ) , and the combined organic layers 
 were dried over na2so4 and concentrated . the 
 residue was purified by silica gel chromatography ( 0.5  4 in . note : for volatile ethers , column 
 fractions were carefully concentrated on a rotary evaporator at 20 
 c bath temperature and then briefly ( 1 min ) concentrated on 
 high vacuum while held in an ice bath . for reaction with grignard 
 reagents , a solution of the alkyl magnesium bromide ( 0.55 mmol , 1.1 
 equiv ) in diethyl ether was added to a 0 c solution of the thp 
 monoperoxyacetal ( 0.5 mmol ) in dry thf ( 3 ml ) . after 15 min , the 
 reaction was quenched with water ( 2 ml ) and extracted with 20% ether / hex 
 ( 1  25 , 1  5 ml ) . the combined organic layers were dried 
 over na2so4 , and the concentrated residue was 
 purified by silica gel chromatography ( 0.5  4 in . , column fractions were 
 concentrated on a rotary evaporator at 20 c bath temperature 
 and subsequently subjected to high vacuum ( < 1 mm ) for 1 min while 
 placed in an ice bath . [ 71077 - 30 - 0 ] : 
 using the general procedure described above , thp monoperoxyacetal 8b ( 128 mg , 0.5 mmol ) was reacted with n - buli 
 ( 0.34 ml , 1.6 m in hex , 0.55 mmol ) to furnish ether 17a as a colorless oil ( 86 mg , 81% ) . the same procedure , when applied 
 to dialkyl peroxide 8b or 2-methoxypropyl peroxyacetal 8c furnished 17a in 70% and 87% yields , respectively . spectral data matched those in previous reports.rf = 0.6 ( 5% ea / hex ) . using the general procedure for grignard - promoted 
 etherification 
 described above , monoperoxacetal 8b ( 128 mg , 0.5 mmol ) 
 was reacted with n - hexyl magnesium bromide ( 0.27 
 ml , 2 m in diethyl ether , 0.55 mmol ) to furnish hexyl ether 17b as a colorless oil ( 106 mg , 88% ) . the same product could 
 be obtained from dialkyl peroxide 8a except in 42% yield : rf = 0.70 ( 10% ea / hex ) ; h nmr : 5.11 
 ( m , 1h ) , 3.473.38 ( m , 4h ) , 2.081.94 ( m , 2h ) , 1.69 
 ( s , 3h ) , 1.651.53 ( m , 4h ) , 1.61 ( s , 3h ) , 1.451.31 
 ( m , 8h ) , 1.231.11 ( m , 1h ) , 0.910.88 ( m , 6h ) ; c nmr : 131.1 , 124.8 , 71.0 , 69.1 , 37.2 , 36.7 , 31.7 , 29.7 , 
 29.6 , 25.9 , 25.7 , 25.4 , 22.6 , 19.6 , 17.6 , and 14.0 . hrms ( tof - ms - ei ) calcd for c16h32o : 240.2453 ; found : 
 240.2453 ; ir : 2954 , 2927 , 2858 , 1455 , 1376 , 1112 . [ 139694 - 24 - 9 ] : to a 0.2 m solution of 
 peroxide 8a ( 229 
 mg , 1.0 mmol ) in thf was added allyltributyl tin ( 0.62 ml , 2.0 mmol ) . the solution was cooled to 78 c , and n - buli ( 2.5 mmol , 1.0 ml , 2.5 m in hex ) was added dropwise . after 
 30 min , the reaction was quenched with 10 ml of water and extracted 
 with ether . the residue was then 
 purified by column chromatography ( 2.5% ea / hex ) to yield 137 mg ( 70% ) 
 of 17c as a colorless oil . the h nmr spectrum 
 matched the listing in a previous report.rf = 0.25 ( 5% ea / hex ) ; h 
 nmr : 0.92 ( d , 3h , j = 6.7 ) , 1.18 ( m , 1h ) , 1.39 ( m , 
 1h ) , 1.521.68 ( s at 1.62 overlapping unresolved signal , 6h ) , 
 1.70 ( s , 3h ) , 2.00 ( m , 2h ) , 3.48 ( m , 2h ) , 3.98 ( dt , 2h , j = 5.6 , 1.4 ) , 5.145.08 ( m 1h ) , 5.19 ( app . dq , hcis , j = 10.6 , 1.3 , 1h ) , 5.29 ( app . dq , htrans , j = 17.2 , 1.6 , 1h ) , 5.9 ( m , 1h ) ; c nmr : 17.6 , 19.6 , 25.5 , 25.7 , 29.6 , 36.7 , 37.2 , 68.7 , 71.8 , 116.7 , 
 124.8 , 131.2 , 135.1 . [ 436141 - 44 - 5 ] : using the general procedure 
 for 
 etherification described above , peroxyacetal 8b ( 128 
 mg , 0.5 mmol ) was reacted with t - buli ( 0.32 ml 1.7 
 m in pentane , 0.55 mmol ) to furnish 17d as a colorless 
 oil ( 55 mg , 51% ) . spectral data were nearly identical to those previously 
 described : rf = 0.6 ( 5% ea / hex ) ; h nmr : 5.11 ( m , 1h ) , 3.423.31 
 ( m , 2h ) , 2.061.91 ( m , 2h ) , 1.69 ( s , 3h ) , 1.61 ( m , 3h ) , 1.591.51 
 ( m , 2h ) , 1.391.27 ( m , 2h ) , 1.19 ( s , 9h ) , 1.171.10 
 ( m , 1h ) , 0.90 ( d , j = 6.5 hz , 3h ) ; c 
 nmr : 131.0 , 124.9 , 72.3 , 59.7 , 37.7 , 37.2 , 29.6 , 27.5 , 25.7 , 25.4 , 
 19.6 , 17.6 . using the general procedure for etherification 
 described above , 
 peroxide 9b ( 118 mg , 0.50 mmol ) was reacted with 2-trimethylsilyl 
 methyl magnesium chloride ( 0.65 ml , 1 m in ether , 0.65 mmol ) to furnish 
 ether 17e as a colorless oil ( 84 mg , 75% ) : rf = 0.8 ( 10% ea / hex ) ; h nmr : 7.317.29 
 ( m , 2h ) , 7.227.19 ( m , 3h ) , 3.42 ( t , j = 6.3 
 hz , 2h ) , 3.12 ( s , 2h ) , 2.70 ( t , j = 7.7 hz , 2h ) , 
 1.911.87 ( m , 2h ) , 0.09 ( s , 9h ) ; c nmr : 142.3 , 
 128.5 , 128.2 , 125.6 , 74.2 , 64.7 , 32.3 , 31.2 , 2.98 ; hrms(tof - ms - ei+ ) 
 calcd for c13h22osi ( m ) : 222.1440 ; 
 found : 222.1442 ; ir : 2955 , 2845 , 1246 , 839 . [ 110458 - 41 - 8 ] : using 
 the general procedure for etherification described above , peroxide 13b ( 115 mg , 0.5 mmol ) was reacted with n - buli ( 0.34 ml 1.6 m in hex , 0.55 mmol ) to furnish ether 17f as a colorless oil ( 73 mg , 78% ) . the h nmr data matched 
 those previously reported : rf = 0.6 ( 5% ea / hex ) ; c nmr : 75.3 , 68.1 , 
 36.7 , 32.3 , 31.8 , 29.4 , 25.6 , 22.6 , 19.7 , 19.4 , 14.0 , 13.9 . [ 51182 - 98 - 0 ] : 
 using the general procedure for etherification using a grignard reagent , 
 peroxide 13b ( 115 mg , 0.50 mmol ) was reacted with n - hexyl magnesium bromide ( 0.27 ml , 2 m in diethyl ether , 
 0.54 mmol ) to furnish hexyl ether 17 g as a colorless 
 oil ( 95 mg , 88% ) . the product has been partially characterized : rf = 0.6 ( 5% ea / hex ) ; h nmr : 3.513.29 ( m , 1h ) , 3.403.29 ( m , 2h ) , 
 1.571.53 ( m , 3h ) , 1.411.29 ( m , 15h ) , 1.12 ( d , j = 6.1 hz , 3h ) , 0.9 ( m , 6h ) ; c nmr : 75.3 , 
 68.4 , 36.7 , 31.8 , 31.7 , 30.1 , 29.4 , 25.9 , 25.6 , 22.63 , 22.62 , 19.7 , 
 14.05 , 14.02 . [ 1927 - 68 - 0 ] : using the general procedure 
 for etherification 
 described above , peroxide 14b ( 101 mg , 0.50 mmol ) was 
 reacted with n - buli ( 0.31 ml 1.6 m in hexane , 0.5 
 mmol ) to furnish ether 17h ( 12 mg , 15% ) accompanied by 
 16 mg ( 15% ) of recovered 14b . partial spectral characterization 
 has been reported.rf = 0.5 ( 15% ea / hex ) ; h nmr : 4.59 ( m , 1h ) , 3.89 
 ( m , 1h ) , 3.76 ( m , 1h ) , 3.52 ( m , 1h ) , 3.40 ( m , 1h ) , 1.84 ( m , 1h ) , 1.72 
 ( m , 1h ) , 1.651.49 ( m , 6h ) , 1.451.35 ( m , 2h ) , 0.94 
 ( t , j = 7.3 hz , 3h ) ; c nmr : 98.8 , 67.3 , 
 62.3 , 31.8 , 30.8 , 25.5 , 19.7 , 1.4 , 13.9 . [ 1927 - 63 - 5 ] using the 
 general procedure for etherification 
 with alkyl magnesium bromide described above , peroxide 14b ( 107 mg , 0.5 mmol ) was reacted with n - hexyl magnesium 
 bromide ( 0.25 ml , 2 m in diethyl ether , 0.50 mmol ) to furnish hexyl 
 ether 17i as a colorless oil ( 57 mg , 61% ) . the h nmr data matched those in a previous report.rf = 0.5 ( 15% ea / hex ) ; h nmr : 4.57 ( m , 1h ) , 3.903.84 ( m , 1h ) , 3.763.70 
 ( m , 1h ) , 3.523.47 ( m , 1h ) , 3.413.35 ( m , 1h ) , 1.871.79 
 ( m , 1h ) , 1.741.68 ( m , 1h ) , 1.621.50 ( m , 6h ) , 1.421.26 
 ( m , 6h ) , 0.89 ( t , j = 6.8 hz , 3h ) ; c 
 nmr : 98.8 , 67.6 , 62.3 , 31.7 , 30.8 , 29.7 , 25.9 , 25.5 , 22.6 , 19.6 , 14.0 . using 
 the general procedure for etherification described above , peroxide 15b ( 107 mg , 0.50 mmol ) was reacted with n - buli ( 0.34 ml , 1.6 m in hex , 0.55 mmol ) to furnish ether 17j as a colorless oil ( 61 mg , 71% ) : rf = 
 0.70 ( 10% ea / hex ) ; h nmr : 3.32 ( t , j = 
 6.4 hz , 2h ) , 1.711.64 ( m , 2h ) , 1.611.45 ( m , 5h ) , 1.431.19 
 ( m , 7h ) , 1.10 ( s , 3h ) , 0.93 ( t , j = 7.20 hz , 3h ) ; c nmr : 72.8 , 59.9 , 36.5 , 32.8 , 25.86 , 24.6 , 22.2 , 19.6 , 13.99 . 
 hrms ( tof - ms - ei ) calcd for c11h22o : 170.1671 ; found : 170.1671 ; ir : 2962 , 2925 , 2862 , 1447 , 1081 . using 
 the general procedure for etherification described above , peroxide 15b ( 107 mg , 0.50 mmol ) was reacted with n - hexyl magnesium bromide ( 0.27 ml , 2 m in ether , 0.54 mmol ) to furnish 
 hexyl ether 17k as a colorless oil ( 64 mg , 65% ) : rf = 0.65 ( 5% ea / hex ) ; h nmr : 3.29 
 ( t , j = 6.7 hz , 2h ) , 1.711.66 ( m , 2h ) , 1.641.47 
 ( m , 5h ) , 1.441.27 ( m , 11h ) , 1.11 ( s , 3h ) , 0.90 ( t , j = 6.9 hz , 3h ) ; c nmr : 72.9 , 60.2 , 36.5 , 31.8 , 
 30.7 , 26.1 , 25.8 , 24.6 , 22.6 , 22.2 , 14.0 ; hrms ( tof - ms - ei ) calcd for c13h26o : 198.1984 ; found : 198.1992 ; 
 ir : 2962 , 2925 , 2862 , 1447 , 1081 . using the general procedure for etherification 
 described above , peroxide 16b ( 135 mg , 0.50 mmol ) was 
 reacted with n - buli ( 0.34 ml , 1.6 m in hex , 0.55 
 mmol ) to furnish ether 17l as a colorless oil ( 86 mg , 
 76% ) : rf = 0.63 ( 10% ea / hex ) ; h nmr : 5.735.66 ( m , 1h ) , 5.595.52 ( m , 1h ) , 4.01 ( m , 
 0.23 h ) , 3.91 ( dd , j = 0.6 , 6.15 , 1.76 h ) , 3.41 ( t , j = 6.6 hz , 2h ) , 2.05 ( m , 2h ) , 1.611.54 ( m , 2h ) , 
 1.431.35 ( m , 4h ) , 1.331.27 ( m , 10h ) , 0.93 ( t , j = 7.4 hz , 3h ) , 0.89 ( t , j = 7.1 hz , 3h ) ; c nmr : 134.5 , 126.4 , 71.6 , 69.8 , 32.3 , 31.88 , 31.87 , 29.4 , 
 29.27 , 29.21 , 29.0 , 22.7 , 19.3 , 14.0 , 13.9 ; hrms ( tof - ms - ei ) : calcd for c15h30o : 226.2297 ; found : 226.2297 ; 
 ir : 2954 , 2923 , 2852 , 1465 , 1105 . using the general procedure for etherification 
 described above , peroxide 16b ( 115 mg , 0.50 mmol ) was 
 reacted with n - hexyl magnesium bromide ( 0.27 ml , 
 2 m in ether , 0.54 mmol ) to furnish hexyl ether 17 m as 
 a colorless oil ( 104 mg , 81% ) : rf = 0.67 
 ( 10% ea / hex ) ; h nmr : 5.735.66 ( m , 1h ) , 5.595.52 
 ( m , 1h ) , 4.01 ( m , 0.24 h ) , 3.91 ( dd , j = 0.6 , 6.2 , 
 1.76 h ) , 3.40 ( t , j = 6.7 , 2h ) , 2.05 ( m , 2h ) , 1.58 
 ( m , 2h ) , 1.431.27 ( m , 18h ) , 0.900.87 ( 6h ) ; c nmr : 134.5 , 126.4 , 71.6 , 70.2 , 32.3 , 31.88 , 31.74 , 29.76 , 29.46 , 
 29.28 , 29.22 , 29.1 , 25.9 , 22.67 , 22.62 , 14.08 , 14.03 . hrms ( tof - ms - ei ) calcd for c17h34o : 254.2610 ; found : 
 254.2610 ; ir : 2954 , 2923 , 2852 , 1465 , 1105 . reactions involving commercially available 
 reagents were conducted as described above for sp c  o bond formations except that reaction times 
 were approximately 1 h. reactions involving in situ formation of vinyl 
 or heteroaryllithium reagents from the corresponding tributylstannanes 
 were conducted as described below . to a 78 c solution 
 of alkenyl- or aryltributyltin ( 0.55 mmol ) in dry thf ( 3 ml ) was added n - buli ( 0.55 mmol , 1.6 m in hex ) . the reaction mixture was 
 stirred for 10 min , after which was added a solution of the monoperoxyacetal 
 ( 0.50 mmol ) in thf ( 1 ml ) . the reaction mixture was stirred until 
 no starting material could be detected on tlc ( approximately 60 min ) 
 and then diluted with hex ( 10 ml ) . the resulting solution was passed 
 though a column of neutral alumina ( 1  2 in . ) and then concentrated 
 ( an aqueous workup could also be conducted employing aq . the residue was purified by silica flash 
 chromatography using 1% ether / hex ; chromatography of enol and thienyl 
 ethers included 0.2% triethylamine . [ 51113 - 53 - 2 ] : using the general 
 procedure described above , peroxide 8b ( 128 mg , 0.5 mmol ) 
 was reacted with phenyl lithium ( 0.30 ml , 1.8 
 m in dibutyl ether , 0.54 mmol ) to furnish phenyl ether 18a as a colorless oil ( 102 mg , 87% ) . the 
 same product was available ( 78 mg , 67% ) by reaction of peroxide 8b ( 128 mg , 0.50 mmol ) with phenyl magnesium bromide ( 0.18 
 ml , 3.0 m in ether , 0.54 mmol ) : rf = 0.66 ( 10% ea / hex ) ; h nmr : 7.327.30 ( m , 2h ) , 
 6.976.93 ( m , 3h ) , 5.15 ( m , 1h ) , 4.03 ( m , 2h ) , 2.08 ( m , 1h ) , 
 2.02 ( m , 1h ) , 1.88 ( m , 1h ) , 1.751.71 ( m , 1h ) , 1.73 ( s , 3h ) , 
 1.65 ( s , 3h ) , 1.641.61 ( m , 1h ) , 1.461.41 ( m , 1h ) , 
 1.301.24 ( m , 1h ) , 0.98 ( d , j = 6.9 hz , 3h ) ; c nmr : 151.1 , 131.3 , 129.4 , 124.7 , 120.5 , 114.5 , 66.1 , 37.2 , 
 36.1 , 29.6 , 25.8 , 25.5 , 19.6 , 17.7 . using the general 
 procedure described above , peroxide 9b ( 118 mg , 0.5 mmol ) 
 was reacted with 2-methyl-1-propenyl 
 magnesium bromide ( 1.3 ml , 0.5 m in thf , 0.65 mmol ) to furnish ether 18b as a colorless oil ( 39 mg , 41% ) , which decomposed during 
 chromatography : h nmr : 7.347.30 ( m , 2h ) , 7.267.21 
 ( m , 3h ) , 5.835.82 ( m , 1h ) , 3.72 ( t , j = 6.4 
 hz , 2h ) , 2.75 ( t , j = 7.8 hz , 2h ) , 2.001.93 
 ( m , 2h ) , 1.68 ( s , 3h ) , 1.59 ( s , 3h ) ; c nmr : 141.8 , 140.0 , 
 128.5 , 128.4 , 125.8 , 110.5 , 70.7 , 32.0 , 31.4 , 19.5 , 15.0 . hrms ( tof - ms - ei ) calcd for c13h18o ( m ) : 
 190.1358 ; found : 190.1363 ; ir : 2918 , 2865 , 1689 , 1496 , 1159 . using the procedure described 
 above for etherifications with in situ 
 generated sp rli , peroxyacetal 8b ( 128 mg , 0.5 mmol ) was reacted with the reagent generated 
 from tributyl vinylstannane ( 237 mg , 0.75 mmol ) and n - buli ( 0.47 ml , 1.6 m in hex , 0.75 mmol ) to furnish ether 18c as a colorless oil ( 62 mg , 66% ) , which partially decomposed upon 
 thin - layer or column chromatography : rf = 0.7 ( 10% ea / hex ) ; h nmr : 6.48 ( dd , j = 6.8 , 14.1 hz , 1h ) , 5.12 ( t , j = 7.0 hz , 1h ) , 
 4.19 ( d , j = 14.1 hz , 1h ) , 3.99 ( d , j = 6.8 hz , 1h ) , 3.783.68 ( m , 2h ) , 2.081.93 ( m , 2h ) , 
 1.771.69 ( m , 1h ) , 1.70 ( s , 3h ) , 1.651.58 ( m , 1h ) , 
 1.62 ( s , 3h ) , 1.541.44 ( m , 1h ) , 1.421.33 ( m , 1h ) , 
 1.251.16 ( m , 1h ) , 0.93 ( d , j = 6.6 hz , 3h ) ; c nmr : 152.0 , 131.3 , 124.7 , 86.2 , 66.3 , 37.1 , 35.9 , 29.5 , 
 25.7 , 25.4 , 19.5 , 17.6 . hrms ( tof - ms - ei calcd for c12h22o ( m  h ) : 181.1598 ; found : 
 181.1602 ; ir : 2961 , 2913 , 2871 , 1647 , 1609 , 1200 . using the procedure described above for 
 etherifications 
 with in situ generated sp rli , peroxyacetal 8b ( 128 mg , 0.50 mmol ) was reacted with the reagent generated 
 from 2-(tributylstannyl)thiophene ( 279 mg , 0.75 mmol ) 
 and n - buli ( 0.47 ml , 1.6 m in hex , 0.75 mmol ) to 
 furnish ether 18d as a colorless oil ( 72 mg , 60% ) : rf = 0.75 ( 10% ea / hex ) ; h nmr : 6.73 
 ( dd , j = 3.7 , 6.0 hz , 1h ) , 6.56 ( dd , j = 1.2 , 6.0 hz , 1h ) , 6.22 ( dd , j = 1.2 , 3.7 hz , 
 1h ) , 5.13 ( t , j = 7.1 hz , 1h ) , 4.104.06 ( m , 
 2h ) , 2.081.98 ( m , 2h ) , 1.891.84 ( m , 1h ) , 1.741.67 
 ( m , 1h ) , 1.72 ( s , 3h ) , 1.64 ( s , 3h ) , 1.621.59 ( m , 1h ) , 1.431.38 
 ( m , 1h ) , 1.271.22 ( m , 1h ) , 0.97 ( d , j = 6.6 
 hz , 3h ) ; c nmr : 165.8 , 131.4 , 124.7 , 124.6 , 111.7 , 104.6 , 
 72.3 , 37.0 , 36.0 , 29.4 , 25.7 , 25.4 , 19.5,17.7 ; hrms ( tof - ms - ei ) calcd for c14h22os ( m ) : 238.1391 ; found : 238.1390 ; ir : 2963 , 2925 , 2913 , 2871 , 1536 , 1193 . using the 
 procedure described above , peroxide 12b ( 129 mg , 0.50 
 mmol ) was reacted with the reagent generated from 2-(tributylstannyl)thiophene 
 ( 279 mg , 0.75 mmol ) and n - buli ( 0.47 ml , 1.6 m in 
 hex , 0.75 mmol ) to furnish ether 18e as a colorless oil 
 ( 65 mg , 54% ) : rf = 0.7 ( 10% ea / hex ) ; h nmr : 6.746.72 ( m , 1h ) , 6.566.54 ( m , 1h ) , 
 6.236.21 ( m , 1h ) , 4.04 ( t , j = 6.4 hz , 2h ) , 
 1.831.76 ( m , 2h ) , 1.481.44 ( m , 2h ) , 1.381.30 
 ( m , 12h ) , 0.91 ( t , j = 6.8 hz , 3h ) ; c nmr : 165.9 , 124.6 , 111.6 , 104.5 , 74.0 , 31.9 , 29.5 , 29.3 , 29.2 , 
 25.8 , 22.7 , 14.1 . hrms ( tof - ms - ei ) calcd for c14h24os ( m ) : 240.1548 ; found : 240.1548 ; ir : 
 2920 , 2853 , 1536 , 1456 , 1193 . the difluoroether was prepared applying 
 a previously reported two - step procedure ( reaction of lithiated dithiane 
 with the peroxide ; fluorodesulfurization of the poorly stable difluoroether 
 products ) to three different precursors : 
 2-(3-phenylpropyl)-1,3-dithiane and monoperoxyacetal 10b ( 100 mg , 51% isolated yield ) ; silyl peroxide 10d ( 105 
 mg , 54% isolated yield ) ; t - butyl peroxide 10a ( 95 mg , 26% , with 35% recovered starting material ) . in each case , 
 difluoroether 19 was isolated as a colorless oil with rf = 0.5 ( 5% ea / hex ) and with spectra matching 
 literature values . [ 123294 - 00 - 8 ] was prepared using a modification 
 of a literature procedure . a solution 
 of diisopropylamine ( 0.22 g , 1.1 equiv ) in 5 ml of thf was cooled 
 to 0 c , and n - buli ( 1.37 ml , 1.6 m in hex , 
 2.2 mmol , 1.1 equiv ) was added . the reaction was stirred for 10 min , 
 after which was added bu3snh ( 0.582 g , 2.0 mmol , 1 equiv ) . the reaction was stirred for 15 min at 0 c and then cooled to 
 78 c , whereupon hydrocinnamaldehyde ( 268 mg , 2.0 mmol ) 
 was added as a solution in thf ( 10 ml ) . after stirring at 78 
 c for 5 min , the 
 separated organic layer was dried over mgso4 and concentrated 
 ( rotary evaporator , followed by high vacuum ) . the residue from 
 the step described above was dissolved in dcm ( 12 ml ) , and the solution 
 cooled to 10 c . diisopropyl ethylamine ( 0.335 g , 1.3 
 equiv ) was added , followed by chloromethyl methyl ether ( 0.177 g , 
 1.1 equiv ) . the reaction was stirred for 7 h at rt and then washed 
 with water ( 10 ml ) . the separated organic layer was dried ( na2so4 ) and concentrated on a rotary evaporator . the 
 residue was chromatographed on silica gel using 1% ea / hex to afford 20 as a colorless liquid ( 63% , 598 mg ) : rf = 0.51 ( 10% ea / hex ) ; h nmr : 7.337.27 
 ( m , 2h ) , 7.237.19 ( m , 3h ) , 4.65 ( d , j = 6.5 
 hz , 1h ) , 4.62 ( d , j = 6.5 hz , 1h ) , 4.154.11 
 ( m , 1h ) , 3.41 ( s , 3h ) , 2.822.66 ( m , 2h ) , 2.222.05 
 ( m , 2h ) , 1.601.49 ( m , 6h ) , 1.391.29 ( m , 6h ) , 0.960.88 
 ( m , 12h ) , 0.92 ( t , j = 7.3 hz , 3h ) ; c nmr : 142.4 , 128.4 , 128.3 , 125.7 , 96.6 , 73.7 , 55.5 , 37.4 , 34.5 , 
 29.2 , 27.5 , 13.7 , 9.2 . to a 78 c solution of stannane 20 ( 235 mg , 0.5 mmol ) in dry thf ( 3 ml ) was added a solution 
 of n - buli in hex ( 1.6 m , 0.5 mmol ) . after the reaction 
 had stirred for 3 min , peroxide 11a ( 100 mg , 0.5 mmol ) 
 was added as a solution in thf ( 1 ml ) , and the reaction was stirred 
 for an additional 30 min at 78 c . the cold bath was 
 removed , and the reaction was allowed to warm to rt over 30 min . the 
 reaction was quenched with water ( 1 ml ) and diluted with hexane ( 40 
 ml ) . the mixture was washed with water ( 10 ml ) , and the separated 
 aqueous layer was extracted with hex ( 10 ml ) . the residue was purified by silica gel chromatography using ether / hex 
 ( 15% ) to furnish recovered 11a ( 10% ) and then 
 the acetal 21a as a colorless oil ( 88 mg , 57% ) : rf = 0.36 ( 10% ea / hex ) ; h nmr : 7.327.27 
 ( m , 2h ) , 7.247.19 ( m , 3h ) , 4.83 ( d , j = 6.8 
 hz , 1h ) , 4.70 ( d , j = 6.8 hz , 1h ) , 4.704.66 
 ( m , 1h ) , 3.683.63 ( m , 1h ) , 3.473.40 ( m , 1h ) , 3.43 
 ( s , 3h ) , 2.712.72 ( m , 2h ) , 2.041.98 ( m , 2h ) , 1.641.57 
 ( m , 2h ) , 1.401.30 ( m , 10h ) , 0.91 ( t , j = 
 6.7 hz , 3h ) ; c nmr : 141.7 , 128.4 , 125.8 , 101.4 , 93.3 , 
 66.7 , 55.7 , 36.4 , 31.8 , 30.8 , 29.8 , 29.4 , 29.2 , 26.2 , 22.6 , 14.1 ; 
 hrms ( esi+ tof ) calcd for c19h32o3 ( m + na ) : 331.2249 ; found : 331.2265 ; ir : 2925 , 2855 , 
 1149 , 1002 . the title compound was synthesized as 
 a colorless 
 oil ( 86 mg , 55% ) from reaction of 9a ( 104 mg , 0.50 mmol ) 
 using the general procedure described above except that 1.2 equiv 
 each of tributylstannane and n - buli was used : rf = 0.43 ( 10% ea / hex ) ; h nmr : 7.357.31 
 ( m , 4h ) , 7.287.21 ( m , 6h ) , 4.85 ( d , , j = 
 6.6 hz , 1h ) , 4.73 ( d , j = 6.6 hz , 1h ) , 4.724.70 
 ( m , 1h ) , 3.743.69 ( m , 1h ) , 3.513.47 ( m , 1h ) , 3.44 
 ( s , 3h ) , 2.812.74 ( m , 4h ) , 2.082.02 ( m , 2h ) , 2.001.93 
 ( m , 2h ) ; c nmr : 141.88 , 141.7 , 128.5 , 128.49 , 128.45 , 
 128.42 , 128.39 , 125.9 , 125.8 , 101.6 , 93.5 , 65.8 , 55.8 , 36.4 , 32.4 , 
 31.4 , 30.8 ; hrms ( tof ms es+ ) calcd for c20h26nao3 ( m + na ) : 337.1780 ; found : 337.1775 ; 
 ir : 2927 , 1453 , 1122 , 1000 , 697 . the title compound was 
 synthesized as a colorless oil 
 ( 89 mg , 53% ) from stannane 20 ( 0.235 g , 0.50 mmol ) and 
 peroxyacetal 12b ( 0.129 g , 0.50 mmol ) using the general 
 procedure described above : rf = 0.40 ( 10% 
 ea / hex ) ; h nmr : 7.307.26 ( m , 2h ) , 7.217.17 
 ( m , 3h ) , 4.824.80 ( m , 1h ) , 4.694.63 ( m , 2h ) , 3.663.60 ( m , 1h ) , 3.40 ( s , 3h ) , 2.742.70 ( m , 2h ) , 2.051.95 
 ( m , 2h ) , 1.601.54 ( m , 2h ) , 1.381.27 ( m , 15h ) , 0.88 
 ( t , j = 6.80 hz , 3h ) ; c nmr : 141.9 , 
 128.4 , 125.9 , 101.5 , 93.4 , 66.9 , 55.8 , 36.4 , 32.0 , 30.9 , 29.9 , 29.7 , 
 29.6 , 29.5 , 29.4 , 26.3 , 22.7 , 14.2 . hrms ( tof ms es+ ) calcd for c21h36nao3 ( m + na ) : 359.2562 ; 
 found : 359.2578 ; ir : 2925 , 2856 , 1149 , 1000 . using the general 
 procedure described above , peroxide 8c ( 244 mg , 0.50 
 mmol ) was reacted with alkoxylithium generated from reaction of stannane 20 ( 235 mg , 0.5 mmol ) and n - buli ( 0.31 ml , 
 1.6 m in hex , 0.5 mmol ) to furnish a mixture of mixed acetal 21d ( 48 mg , 28% ) accompanied by 3-methoxymethyloxy-2-methyl-5-phenylpentan-2-ol 22 ( 23 mg , 20% ) . nmr analysis of the crude reaction mixture 
 suggested the presence of 40% of mixed acetal 21d ; presumably , 
 some was lost during the separation process . the mixed acetal 16d was contaminated with a small amount of inseparable byproduct , 
 which could be removed by subjecting a dcm solution of the crude reaction 
 mixture to brief ( 1 min ) room temperature ozonolysis with 
 2% o3/o2 ( 1 mmol o3/min ) prior to 
 chromatography . the separated byproduct was determined to be 3-methoxymethoxypropyl 
 benzene ( 3 mg , 3% ) , the product of protonation of the functionalized 
 organolithium reagent . rf = 0.5 
 ( 5% ea / hex ) ; h nmr : 7.327.27 ( m , 2h ) , 7.237.19 
 ( m , 3h ) , 5.12 ( m , 1h ) , 4.83 ( d , j = 6.8 hz , 1h ) , 
 4.70 ( d , j = 6.8 hz , 1h ) , 4.684.66 ( m , 1h ) , 
 3.733.64 ( m , 1h ) , 3.523.44 ( m , 1h ) , 3.43 ( s , 3h ) , 
 2.74 ( m , 2h ) , 2.081.91 ( m , 4h ) , 1.70 ( s , 3h ) , 1.681.56 
 ( m , 2h ) , 1.62 ( s , 3h ) , 1.491.31 ( m , 2h ) , 1.281.14 
 ( m , 1h ) , 0.930.91 ( m , 3h ) ; c nmr : 141.7 , 131.2 , 
 128.4 , 128.4 , 128.39 , 125.8 , 124.7 , 101.5 , 101.4 , 93.3 , 64.9 , 64.8 , 
 55.7 , 37.2 , 37.1 , 36.8 , 36.78 , 36.39 , 30.83 , 29.5 , 25.7 , 25.5 , 19.6 , 
 19.5 , 17.6 ; hrms ( tof - esi ) calcd for c21h34o3na ( m + na ) : 357.2406 ; found 357.2401 ; 
 ir : 2927 , 1454 , 1369 , 1002 . rf = 0.3 ( 15% 
 ea / hex ) ; h nmr : 7.337.27 ( m , 2h ) , 7.227.20 
 ( m , 3h ) , 
 4.84 ( d , j = 6.7 hz , 1h ) , 4.69 ( d , j = 6.7 hz , 1h ) , 3.58 ( s , 1h ) , 3.49 ( s , 3h ) , 3.29 ( m , 1h ) , 2.942.87 
 ( m , 1h ) , 2.662.58 ( m , 1h ) , 1.881.81 ( m , 1h ) , 1.781.70 
 ( m , 1h ) , 1.19 ( s , 3h ) , 1.15 ( s , 3h ) ; c nmr : 141.9 , 128.5 , 
 128.4 , 125.9 , 99.2 , 89.9 , 72.0 , 56.0 , 33.5 , 32.7 , 26.3 , 23.7 . hrms 
 ( tof - esi ) calcd for c14h22o3na ( m + na ) : 261.1467 ; found : 261.1483 ; ir : 3461 , 
 2930 , 2889 , 1028 . 3-methoxymethoxypropylbenzene [ 91898 - 11 - 2 ] 
 has been reported on multiple occasions without nmr characterization : rf = 0.5 ( 20% ea / hex ) ; h nmr : 7.337.28 
 ( m , 2h ) , 7.237.18 ( m , 3h ) , 4.66 ( s , 3h ) , 3.57 ( t , j = 6.4 hz , 2h ) , 3.39 ( s , 3h ) , 2.73 ( t , j = 7.8 hz , 2h ) , 1.991.89 ( m , 2h ) ; c nmr : 141.9 , 
 128.4 , 128.3 , 125.8 , 96.5 , 67.1 , 55.2 , 32.4 , 31.4 . the thp monoperoxyacetal 
 ( 0.50 mmol ) was dissolved in dry thf ( 5 
 ml ) , and the solution cooled to 0 c . cyclopropyl magnesium bromide 
 ( 1.3 ml , 0.5 m in thf , 0.65 mmol ) was then added . the cooling bath 
 was removed , and the reaction was stirred for 45 min prior to quenching 
 by sequential dilution with 1 m aq . the combined hex extracts ( 20 ml  2 ) were dried over 
 na2so4 and concentrated on a rotary evaporator . diameter ) using 12% ea / hex , with fraction concentrated 
 initially at 80120 mm . ( rotary evaporator , rt ) and at 0.5 
 mm ( 1 min , 0 c ) . using the general procedure described 
 above , thp peroxide 8b ( 128 mg , 0.50 mmol ) was reacted 
 with cyclopropyl magnesium 
 bromide ( 1.3 ml , 0.5 m in thf , 0.65 mmol ) to furnish cyclopropyl ether 23a as a colorless oil ( 80 mg , 80% ) : rf = 0.52 ( 10% ea / hex ) ; h nmr : 5.135.09 
 ( m , 1h ) , 3.583.48 ( m , 2h ) , 3.283.24 ( m , 1h ) , 2.051.91 
 ( m , 2h ) , 1.70 ( s , 3h ) , 1.62 ( s , 3h ) , 1.581.49 ( m , 2h ) , 1.421.31 
 ( m , 2h ) , 1.231.09 ( m , 1h ) , 0.91 ( d , j = 6.5 
 hz , 3h ) , 0.580.54 ( m , 2h ) , 0.480.43 ( m , 2h ) ; c nmr : 131.1 , 124.8 , 68.9 , 52.9 , 37.2 , 36.6 , 29.5 , 25.7 , 
 25.4 , 19.5 , 17.6 , 5.45 , 5.41 ; hrms ( tof - ms ci ) calcd for 
 c13h25o ( m + h ) : 197.1905 ; found : 
 197.1913 ; ir : 2960 , 2916 , 1452 , 1342 . using the general procedure described 
 above , thp peroxide 9b ( 118 mg , 0.50 mmol ) was reacted 
 with cyclopropyl magnesium bromide 
 ( 1.3 ml , 0.5 m in thf , 0.65 mmol ) to furnish cyclopropyl ether 23b as a colorless oil ( 64 mg , 72% ) : rf = 0.46 ( 10% ea / hex ) ; h nmr : 7.327.29 
 ( m , 2h ) , 7.227.19 ( m , 3h ) , 3.52 ( t , j = 6.4 
 hz , 2h ) , 3.28 ( app septet , likely tt , j = 3.0 , 6.0 
 hz , 1h ) , 2.70 ( t , j = 7.7 hz , 2h ) , 1.941.87 
 ( m , 2h ) , 0.610.57 ( m , 2h ) , 0.490.45 ( m , 2h ) ; c nmr : 141.9 , 128.4 , 128.3 , 125.8 , 69.7 , 53.0 , 32.4 , 31.2 , 
 5.5 ; hrms : ( tof - ms ei ) calcd for c12h16o ( m ) : 176.1201 ; found : 176.1199 ; ir : 3031 , 2938 , 2850 , 
 1452 , 1342 . using the 
 general procedure described above , thp peroxide 12b ( 129 
 mg , 0.50 mmol ) was reacted with cyclopropyl magnesium bromide ( 1.3 
 ml , 0.5 m in thf , 0.65 mmol ) to furnish cyclopropyl ether 23c as a colorless oil ( 79 mg , 80% ) : rf = 
 0.56 ( 10% ea / hex ) ; h nmr : 3.49 ( t , j = 
 6.7 hz , 2h ) , 3.26 ( app septet , likely tt , j = 3.0 , 
 6.0 hz , 1h ) , 1.581.54 ( m , 2h ) , 1.341.27 ( m , 14h ) , 
 0.89 ( t , j = 7.0 hz , 3h ) , 0.570.55 ( m , 2h ) , 
 0.471.95 ( m , 2h ) ; c nmr : 70.7 , 52.9 , 31.9 , 29.68 , 
 29.60 , 29.57 , 29.5 , 29.3 , 26.2 , 22.7 , 14.1 , 5.4 ; hrms : ( tof - ms ci ) calcd for c13h27o ( m + h ) : 199.2062 ; found : 199.2057 ; ir : 2922 , 2853 , 1453 , 1343 . using the 
 general procedure described above , thp peroxide 13b ( 115 
 mg , 0.50 mmol ) was reacted with cyclopropyl magnesium bromide ( 1.3 
 ml , 0.5 m in thf , 0.65 mmol ) to furnish cyclopropyl ether 23d as a colorless oil ( 60 mg , 70% ) : rf = 
 0.6 ( 10% ea / hex ) ; h nmr : 3.573.49 ( m , 1h ) , 3.333.29 
 ( m , 1h ) , 1.411.23 ( m , 10h ) , 1.18 ( d , j = 
 6.1 hz , 3h ) , 0.89 ( t , j = 6.8 hz , 3h ) , 0.610.56 
 ( m , 1h ) , 0.540.51 ( m , 1h ) , 0.490.47 ( m , 1h ) , 0.460.40 
 ( m , 1h ) ; c nmr : 75.7 , 50.7 , 36.6 , 31.8 , 29.4 , 25.4 , 22.6 , 
 19.9 , 14.0 , 5.96 , 5.42 ; hrms ( tof - ms ei ) calcd for c11h22o ( m ) : 170.1671 ; found : 170.1678 ; 
 ir : 2927 , 2857 , 1452 , 1373 . [ 133476 - 12 - 7 ] : 2-bromo-2-methylpropyl benzene [ 23264 - 13 - 3 ] was prepared ( 3.79 g , 88% ) as a colorless liquid 
 from the corresponding alcohol ( 3 g , 20 mmol ) using a modification 
 of a reported procedure . spectral data 
 matched those in a previous report.rf = 0.8 ( 25% ea / hex ) ; h nmr : 7.357.26 
 ( m , 5h ) , 3.22 ( s , 2h ) , 1.78 ( s , 6h ) ; c nmr : 137.3 , 130.9 , 
 128.0 , 127.0 , 66.6 , 53.4 , 33.9 . the t - buyl 
 peroxide was prepared from the bromide ( 1.89 g 8.9 mmol , 1 equiv ) 
 through reaction with t - buooh ( 1.94 ml , 5.5 m in 
 decane 1.2 equiv , 10.6 mmol ) , and silver trifluoroacetate ( 2.34 g , 
 10.6 mmol 1.2 equiv ) using a reported procedure . following a workup which includes brief exposure to nabh4 to destroy the trifluoroacetate ester , peroxide 24a was isolated as a colorless oil ( 0.79 g , 40% ) , which was only modestly 
 responsive to the  peroxide  tlc stain ( see the general experimental section ) even after warming : rf = 0.7 ( 10% ea / hex ) . [ 830345 - 47 ] : 2-methyl-3-phenyl-1-propene 
 ( 0.66 g , 5 mmol ) and et3sih ( 1.16 g , 10 mmol ) were sequentially 
 added to a solution of co(acac)2 ( 0.50 mmol ) in ethanol 
 ( 15 ml ) . the reaction mixture was stirred 
 under an atmosphere of o2 ( balloon ) until no starting material 
 was observed ( tlc , 14 h ) . the residue obtained upon concentration 
 in vacuo was purified by silica gel chromatography using 18% 
 ea / hex to furnish 24d ( 0.95 g , 68% ) as a colorless oil . the molecule has previously been reported without nmr characterization : rf = 0.7 ( 10% ea / hex ) ; h nmr : 7.287.18 ( m , 5h ) , 2.88 ( s , 2h ) , 1.16 ( s , 6h ) , 
 1.00 ( m , j = 7.9 hz , 9h ) , 0.70 ( q , j = 7.9 hz , 6h ) ; c nmr : 138.3 , 130.8 , 127.8 , 126.1 , 82.6 , 
 44.8 , 24.3 , 6.9 , 4.0 . to a 0 c 
 solution of silyl peroxide 24d ( 0.70 g , 2.5 mmol ) in 
 thf ( 6 ml ) was added n - bu4nf ( 3 ml , 1 
 m in thf , 3 mmol ) . after 10 min , the reaction was diluted 
 with 50 ml of hex and the resulting solution was washed with water 
 ( 2  5 ml ) . the dried ( na2so4 ) organic 
 layer was concentrated , and the residue was purified through a short 
 plug of silica ( 10% ea / hexane ) to furnish 2-hydroperoxy-2-methylpropyl)benzene 
 [ 1944 - 83 - 8 ] as a colorless oil ( 0.41 g , 98% ) , which displayed spectral 
 data matching literature reports.rf = 0.35 ( 10% ea / hex ) . the crude hydroperoxide 
 ( 0.40 g , 2.4 mmol ) and dihydropyran ( 0.2 g , 2.4 mmol ) were reacted 
 using method b to furnish monoperoxyacetal 24b as a colorless 
 oil ( 0.397 g , 66% ) : rf = 0.42 ( 10% ea / hex ) ; h nmr : 7.297.19 ( 5h ) , 5.12 ( m , 1h ) , 4.06 ( m , 1h ) , 
 3.63 ( m , 1h ) , 2.97 ( d , j = 13.5 hz , 1h ) , 2.86 ( d , j = 13.5 hz , 1h ) , 1.79175 ( m , 2h ) , 1.671.59 
 ( m , 4h ) , 1.25 ( s , 3h ) , 1.18 ( s , 3h ) ; c nmr : 138.0 , 130.7 , 
 127.9 , 126.2 , 101.2 , 82.9 , 62.8 , 45.0 , 27.9 , 25.3 , 24.7 , 24.3 , 20.1 . 
 hrms ( tof - ms - es+ ) calcd for c15h22nao3 ( m + na ) : 273.1461 ; found : 273.1461 ; ir : 2928 , 2856 , 1451 . reaction of monoperoxyacetal24bwith organometallic reagents . using the procedure described for reaction of n - buli 
 with thp monoperoxyacetals , reaction of 24b ( 125 mg , 
 0.50 mmol ) with n - buli ( 0.34 ml , 1.6 m in hex , 0.55 
 mmol ) at 78 c for 15 min furnished , after workup and chromatography , 
 recovered 24b ( 9 mg , 7% ) , alcohol 26 ( 15 
 mg , 10% ) , and butyl ether 25a ( 56 mg , 55% ) . colorless oil ; rf = 0.75 ( 10% 
 ea / hex ) ; h nmr : 7.297.26 
 ( m , 2h ) , 7.237.19 ( m , 3h ) , 3.42 ( t , j = 6.6 
 hz , 2h ) , 2.79 ( s , 2h ) , 1.591.52 ( m , 2h ) , 1.441.35 
 ( m , 2h ) , 1.14 ( s , 6h ) , 0.94 ( t , j = 7.3 hz , 3h ) ; c nmr : 138.8 , 130.7 , 127.8 , 126.0 , 74.9 , 61.2 , 47.2 , 32.8 , 
 25.3 , 19.6 , 14.1 ; hrms ( tof ms ei+ ) calcd for c14h22o ( m ) : 206.1671 ; found : 206.1677 ; ir : 2956 , 2927 , 
 1453 , 1362 , 1080 . by the general procedure described for reaction 
 of grignard reagents 
 with monoperoxyacetals , a solution of 24c ( 125 mg , 0.5 
 mmol ) in thf ( 3 ml ) was reacted with hexylmgbr ( 0.60 ml , 2 m in ether , 
 2.4 equiv ) to furnish , after workup and chromatography , hexyl ether 25b as a colorless oil ( 88 mg , 75% ) : rf = 0.75 ( 10% ea / hex ) ; h nmr : 7.297.25 
 ( m , 2h ) , 7.227.19 ( m , 3h ) , 3.41 ( t , j = 6.7 
 hz , 2h ) , 2.78 ( s , 2h ) , 1.601.52 ( m , 2h ) , 1.391.30 
 ( m , 6h ) , 1.14 ( s , 6h ) , 0.91 ( t , j = 6.8 hz , 3h ) ; c nmr : 138.8 , 130.7 , 127.8 , 126.0 , 74.9 , 61.5 , 47.1 , 31.9 , 
 30.7 , 26.1 , 25.3 , 22.7 , 14.2 . hrms calcd for c16h26ona ( m + na ) : 257.1879 ; found : 257.1881 ; ir : 2956 , 2927 , 
 1453 , 1362 , 1080 . using 
 the general procedure 
 described for reaction of n - buli with thp peroxides 
 as above , peroxide 24a ( 222 mg , 1.0 mmol ) was reacted 
 with n - buli ( 0.62 ml , 1.6 m in hex , 1.1 mmol ) at 
 room temperature for 5 h to furnish , following workup and chromatography , 
 the following products : unreacted starting material ( 101 mg , 45% ) ; 
 alcohol 26 ( 48 mg , 32% ) ; and pentylbenzene ( 5 mg , 3% ) : 2-methyl-1-phenylpropan-2-ol ( 26 ) [ 100 - 86 - 7 ] : colorless oil ; rf = 0.35 ( 10% ea / hex ) ; h nmr : 7.337.21 
 ( m , 5h ) , 2.77 ( s , 2h ) , 1.23 ( s , 6h ) ; c nmr : 137.9 , 130.5 , 
 128.3 , 126.6 , 70.8 , 49.8 , 29.2 . pentyl benzene [ 538 - 68 - 1 ] : 
 colorless oil ; rf = 0.8 ( 10% ea / hex ) ; h nmr : 7.317.29 ( m , 2h ) , 7.237.19 ( m , 3h ) , 
 2.63 ( t , j = 7.7 hz , 2h ) , 1.671.62 ( m , 2h ) , 
 1.401.33 ( m , 4h ) , 0.93 ( t , j = 7.0 hz , 3h ) ; c nmr : 142.9 , 128.4 , 128.2 , 125.5 , 35.9 , 31.5 , 31.2 , 22.5 , 
 14.0 . peroxide 24d ( 280 mg , 1.0 mmol ) 
 was reacted with n - buli ( 0.62 ml , 1.6 m in hex , 1 
 mmol ) at room temperature for 6 h , to furnish a mixture of products 
 which were separated by chromatography : recovered 24d ( 115 mg , 41% ) ; et3sioh ( 15 mg , 24% ) ; pentylbenzene ( 16 
 mg , 11% ) and alcohol 26 ( 15 mg , 10% ) . colorless oil ; rf = 
 0.5 ( 10% ea / hex ) ; h nmr : 1.491.44 
 ( bs , 1h ) , 0.99 ( t , j = 8.0 hz , 9 h ) , 0.618 ( q , j = 8.0 hz , 6h ) ; c nmr : 6.58 , 5.79 . to a 78 c solution containing peroxyacetal 12b ( 0.50 mmol , 129 mg ) and peroxide 9a ( 0.50 
 mmol , 104 mg ) in thf ( 3 ml ) was added n - buli ( 0.31 
 ml , 1.6 m in hex , 0.50 mmol ) . the reaction was quenched after 3 min 
 with an excess of water to furnish , as a colorless oil , n - butyl decyl ether ( 27 , 70 mg , 65% ) accompanied by recovered 9a ( 90 mg , 86% ) . butyl decyl ether ( 27 ) [ 111082 - 32 - 7 ] : rf = 0.8 ( 10% ea / hex ) ; h nmr : 3.413.37 ( m , 4h ) , 1.611.51 ( m , 4h ) , 
 1.411.26 ( m , 16h ) , 0.91 ( t , j = 7.4 hz , 3h ) ; 
 0.87 ( t , j = 6.8 hz , 3h ) ; c nmr : 71.1 . 
 70.7 , 32.02 . 32.00 , 29.9 , 29.73 , 29.69 , 29.62 , 29.4 , 26.3 , 22.8 , 19.5 , 
 14.2 , 14.0 . solutions of n - buli ( 0.47 ml , 0.762 
 mmol , 1.6 m in hex ) and phli ( 0.42 ml , 0.762 mmol , 1.8 m in dibutyl 
 ether , 0.42 ml ) were sequentially drawn into the same 1 ml syringe , 
 and the contents were rapidly added to a rapidly stirring 78 
 c solution of 9b ( 0.762 mmol , 180 mg ) in dry thf 
 ( 5 ml ) . the reaction was quenched at 78 c after 5 min to furnish 
 dialkyl ether 28 ( 78 mg , 53% ) , phenyl alkyl ether 29 ( 30 mg , 19% ) , and biphenyl ( 5 mg , 4% ) : 3-butoxypropyl 
 benzene ( 28 ) : spectral data were nearly identical 
 to those previously reported.rf = 0.7 ( 10% ea / hex ) ; h nmr : 7.327.28 
 ( m , 2h ) , 7.237.20 ( m , 3h ) , 3.463.43 ( m , 4h ) , 2.72 
 ( t , j = 7.6 hz , 2h ) , 1.951.91 ( m , 2h ) , 1.631.57 
 ( m , 2h)1.441.40 ( m , 2h ) , 0.96 ( t , j = 7.4 
 hz , 3h ) ; c nmr : 142.1 , 128.5 , 128.3 , 125.7 , 70.7 , 69.9 , 
 32.4 , 31.9 , 31.3 , 19.4 , 14.0 . 3-phenoxy propyl benzene [ 64806 - 63 - 9 ] ( 29 ) : colorless oil ; rf = 0.6 ( 10% ea / hex ) ; h nmr : 7.347.21 
 ( m , 7h ) ; 6.996.92 ( m , 3h ) ; 4.00 ( t , j = 6.3 
 hz , 2h ) , 2.85 ( t , j = 7.5 hz , 2h ) , 2.18 ( m , 2h ) ; c nmr : 159.1 , 141.7 , 129.5 , 128.6 , 128.5 , 126.0 , 120.7 , 114.7 , 
 66.9 , 32.3 , 30.9 . using the 
 general procedure for etherification described above , methoxyethoxy 
 peroxide 9e ( 105 mg , 0.5 mmol ) was reacted with n - buli ( 0.34 ml , 1.6 m in hex , 0.55 mmol ) to furnish 3-butoxypropyl 
 benzene ( 28 , 25 mg , 26% ) as a colorless oil , accompanied 
 by a small amount ( 4 mg , 6% ) of 3-phenyl-1-propanol . although 
 no safety issues were encountered in the course of this work , any 
 preparative work with peroxides should be conducted with an awareness 
 of the potential for spontaneous and exothermic decomposition reactions . the reader is directed to a web - published collection of peroxide - related 
 safety information .
although transfer of electrophilic 
 alkoxyl (  ro+  ) 
 from organic peroxides to organometallics offers a complement to traditional 
 methods for etherification , application has been limited by constraints 
 associated with peroxide reactivity and stability . 
 we now demonstrate 
 that readily prepared tetrahydropyranyl monoperoxyacetals react with sp3 and sp2 organolithium 
 and organomagnesium reagents to furnish moderate to high yields of 
 ethers . the method is successfully applied to the synthesis of alkyl , 
 alkenyl , aryl , heteroaryl , and cyclopropyl ethers , mixed o , o - acetals , and s , s , o - orthoesters . 
 in contrast to reactions of dialkyl 
 and alkyl / silyl peroxides , the displacements of monoperoxyacetals 
 provide no evidence for alkoxy radical intermediates . at the same 
 time , the high yields observed for transfer of primary , secondary , 
 or tertiary alkoxides , the latter involving attack on neopentyl oxygen , 
 are inconsistent with an sn2 mechanism . 
 theoretical studies 
 suggest a mechanism involving lewis acid promoted insertion of organometallics 
 into the o  o bond .