bluuebunny/crossref_metadata_2025_split huggingface dataset:
Performance evaluation of minimum S/N loss pulse compression filter with zero range sidelobe applied to phase‐coded waveforms
Authors: Shinonaga Mitsuyoshi , Yajima Shinichi , Nishimoto Shinkichi 
Published: November 2005

AbstractA new pulse compression filter design technique to realize theoretical minimum S/N loss with zero range sidelobe was indicated in our previous paper. In succession, we have verified in this paper the performance of this pulse compression filter applied to discrete phase‐coded waveforms modulated by Barker code or P4 code via numerical simulations. As a result, we have concluded that the filter derived by our proposed formula surely realizes zero range sidelobe even in the case of oversampling in one code chip, the compressed pulse width is almost the same as the code chip length, and the degradation caused by the Doppler effect is inevitable but equivalent to traditional pulse compression filters. © 2005 Wiley Periodicals, Inc. Electron Comm Jpn Pt 1, 89(3): 10–20, 2006; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/ecja.20263
Heat denaturation, a simple method to improve the immunotherapeutic potential of allergens
Authors: Johansen Pål , Senti Gabriela , Martínez Gómez Julia Maria , Wüthrich Brunello , Bot Adrian , Kündig Thomas M. 
Published: November 2005

AbstractAllergen‐specific immunotherapy (SIT) leads to a long‐term amelioration of IgE‐ and Th2‐mediated allergic diseases. However, SIT efficiency is low, with years of treatment along with frequent allergic side effects. The goal of this study was to reduce the side effects by destroying IgE‐binding epitopes, i.e. by heat‐denaturation, while preserving the therapeutic effect. Mice were immunised with bee venom, birch pollen, grass pollen or cat hair allergens, or with ovalbumin. Heat‐denatured allergens bound less IgE but enhanced Th1‐dependent IgG2a production as measured by ELISA. The strong IgG2a antibody responses also prevented allergic anaphylaxis in mice, as measured by body temperature drop after a challenge with a high allergen dose. We found that optimal heat‐denaturation of allergens left a small proportion in the native conformation to sufficiently stimulate B cells, while non‐B cell‐mediated effects were probably amplified. The enhanced immunogenicity of heat‐denatured allergens is likely explained by enhanced antigen presentation to T cells due to the particulate nature of heat‐denatured proteins. This enables Th1 skewing of the immune response with strong production of IgG2a in mice. Therefore, heat‐denaturation represents probably the simplest way to enhance the efficiency of SIT while reducing its side effects.
Mechanism of Isomerization of Ni(cyclam) in Aqueous Solutions
Authors: Maimon Eric , Zilbermann Israel , Cohen Haim , Kost Daniel , van Eldik Rudi , Meyerstein Dan 
Published: November 2005

AbstractNickel complexes of cyclam and cyclam derivatives isomerize in aqueous solutions via two different mechanisms: i. deprotonation of one of the coordinated amino groups followed by inversion and ii. cleavage of the Ni–N bond followed by inversion. While the first mechanism is relevant for the di‐ and tri‐valent nickel complexes, the second one occurs for the mono‐valent complexes, and for complexes with tertiary amines as ligands. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Catechol Oxidation with Dinuclear Copper Complexes of Aliphatic Tripodal Amino Alcohols
Authors: Jocher Christoph , Pape Tania , Seidel Wolfram W. , Gamez Patrick , Reedijk Jan , Hahn F. Ekkehardt 
Published: November 2005

AbstractA set of unsymmetrical tripodal (aminoalkyl)bis(hydoxyalkyl)amine ligands H4‐2 to H4‐6 with either ethyl or propyl ligand arms has been prepared and characterized. These ligands react with copper hydroxide and ammonium hexafluorophosphate, copper(II) bromide or tris(triphenylphosphane)copper(I) bromide to give di‐ and polynuclear complexes. The dinuclear copper complexes 9a–f catalyze the oxidation of 3,5‐di‐tert‐butylcatechol (DTBC). The coordination geometry at the copper center is influenced by the length of the side arms resulting in a different reactivity of complexes 9a–f in the DTBC oxidation. Alternative preparation procedures lead in selected cases to the formation of coordination polymers 10a and 10b. The reversible formation of the poly(dinuclear) cations in 10a illustrates that the apical alcohol groups are labile. The solid‐state structures are neither necessarily identical with solution structure nor do they represent the catalytically active species. Electronic spectra, however, agree with a dinuclear structures in solution as indicated by the characteristics of the oxygen–copper‐CT. The observation of comparable catalytic activities for complexes 9a–9d renders the bridging coordination of the catechol by both copper ions of a dinuclear complex moiety unlikely. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Reactions of Furylruthenium Complexes with Oxygen and Trimethylsilyl Azide
Authors: Chang Ku‐Hsien , Sung Hui‐Ling , Lin Ying‐Chih 
Published: November 2005

AbstractThe reaction of the (α‐alkoxyfuryl)ruthenium complexes 4 with oxygen opens the five‐membered furyl ring to give the addition product [Ru]O2CCR=CHCO2CH3, (5, [Ru] = Cp(PPh3)2Ru). Further reactions of 5 with CH3I and with organic acid gave CH3O2CCR=CHCO2CH3, (6), and HO2CCR=CHCO2CH3, (7), respectively. The reaction of 4 with TMSN3 [TMS = (CH3)3Si] gives the ruthenium azide [Ru]–N3 and α‐alkoxyfuran, which is readily hydrolyzed to lactone in acidic medium. Treatment of the cyclopropenylruthenium complex 11b containing a methyl crotonate group with TMSN3 affords the five‐membered‐ring triazole and [Ru]–CN. In this reaction cleavage of the C=C double bond of the three‐membered ring could be caused by consecutive additions of TMSN3 to olefinic carbon atoms of intermediates formed during the reaction.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Theoretical Study of the Effects of Phosphane Substituents on the Bonding Properties of Acetylene with Ni(PR3)2 (R = H, CH3, F, CF3, C6H5)
Authors: Piacenza Manuel , Rakow Julia , Hyla‐Kryspin Isabella , Grimme Stefan 
Published: November 2005

AbstractThe bond‐formation processes between the d10 metal fragments Ni(PR3)2 (R = H, CH3, F, CF3, Ph) and acetylene have been studied by density functional theory with the BP86 functional and large TZV(2df,2pd) basis sets. The Ni–acetylene bonds have been analyzed in terms of distortion and intrinsic interaction energies within the Dewar–Chatt–Duncanson model of bonding. The intrinsic interaction energies have been corrected for basis set superposition error (BSSE). Linear relationships have been found between the intrinsic interaction energies and the distances of the Ni–C and C≡C bonds as well as with the acetylene–nickel π‐backbonding. No linear relationship with respect to the total interaction energies was found. Despite using large basis sets, BSSE still contaminates the interaction energies by 5–10 %. For the PR3 ligands, the BSSE‐corrected intrinsic interaction energies of acetylene bonding increase in the order P(CF3)3 < PF3 < PPh3 < PH3 < P(CH3)3 from 58.9 to 77.9 kcal mol–1, while the total interaction energies range from 32.9 to 42.4 kcal mol–1 in the order PPh3 < P(CF3)3 < P(CH3)3 < PH3 < PF3. These results reveal that the total influence of PH3 and PPh3 on the thermodynamics of the acetylene bonding is different and therefore in this sense PH3 is not a good model of PPh3 in theoretical calculations.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Reactivity of the Inversely Polarized Arsaalkenes R–As=C(NMe2)2 {R = [(η5‐C5Me5)(CO)2Fe], tBuC(O), 4‐Et–C6H4C(O)} towards Phosphavinylidene Complexes [η5‐(C5H5)(CO)2M=P=C(SiMe3)2] (M = Mo, W)
Authors: Weber Lothar , Bayer Philipp , Uthmann Stefan , Braun Thomas , Stammler Hans‐Georg , Neumann Beate 
Published: November 2005

AbstractThe reaction of the phosphavinylidene complexes [Cp(CO)2M=P=C(SiMe3)2] [Cp = C5H5, M = Mo (2), W (3)] with the ferrioaarsaalkene [Cp*(CO)2Fe–As=C(NMe2)2] (1a) (Cp* = C5Me5) afforded the novel η3‐2‐phospha‐1‐arsaallyl complexes [η3‐{[Fe]–As–P–C(SiMe3)2}M(CO)2Cp] {M = Mo, [Fe] = [Cp*(CO)2Fe] (4a);W (5a)}. Similarly, treatment of equimolar amounts of 3 with arsaalkene tBu–C(O)–As=C(NMe2)2 (1b) gave rise to the formation of [η3‐{tBuC(O)–As–P–C(SiMe3)2}W(CO)2Cp] (5b) by an arsinidene transfer process. In contrast to this, the more reactive arsaalkene 4‐Et–C6H4C(O)–As=C(NMe2)2 (1c) and complex 3 underwent reaction to give the cyclic phosphenium complex [Cp(CO)2W=P–O–Ca(4‐Et–C6H4)=As–Cb(SiMe3)2(P–Cb)] (6). The novel compounds 4a, 5a, 5b, and 6 were characterized by elemental analyses and by means of spectroscopy (IR, 1H, 13C, 31P NMR). Moreover, the molecular structures of 4a, 5b, and 6 were elucidated by X‐ray diffraction analyses.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Enantiopure Ruthenocenes Cp*Ru(1,2‐C5H3R1R2) with a Planar Chiral Cyclopentadienyl Ligand and a Pentamethylcyclopentadienyl Spectator Ligand
Authors: Herberich Gerhard E. , Englert Ulli , Wirth Tobias 
Published: November 2005

AbstractKreutzberger’s synthesis was used to produce 6‐(morpholino)fulvene (7a) from 1,3,5‐triazine, cyclopentadiene and morpholine (94 %). Likewise with (S)‐2‐(methoxymethyl)pyrrolidine (HSMP) the 6‐[(S)‐2‐(methoxymethyl)pyrrolidino] analogue 7b was obtained (62 %). Hydride addition from NaBHEt3 in toluene afforded the cyclopentadienides Na[C5H4CH2–N(C2H4)2O] (8a) (83 %) and Na(C5H4CH2–SMP) (8b) (90 %). Cp*Ru(C5H4CH2–SMP) (5) was synthesized from [Cp*RuCl]4 and 8b (84 % yield). The related methyleneiminium salt [Cp*Ru(C5H4CH=SMP)]PF6 (9) was made from [Cp*Ru(MeCN)3]PF6 and 7b and could be transformed into 5 by hydride addition from LiAlH4 in THF. Diastereoselective lithiation of 5 with LisBu in Et2O/cyclohexane and subsequent quenching with electrophiles E–X gave enantiomerically pure (de > 98 %), 1,2‐disubstituted complexes Cp*Ru(E–C5H3CH2–SMP) 10a–i with E = F, Cl, Br, I, Me, CD3, SiMe3, PPh2, Au(PPh3) as oils. The chiral auxiliary was removed from 10a, b, and f by quaternization with MeI and subsequent reductive cleavage with LiAlH4 in THF to afford the exclusively planar chiral complexes Cp*Ru(1‐E‐2‐MeC5H3) 14a (E = F), 14b (E = Cl), and 14f (E = CD3). The complexes 14a,b,f no longer possess central chirality. The crystal structure of 12, a LiI adduct of 10f, gave the absolute configuration via internal reference to the (S)‐stereochemistry of the SMP group. The absolute configuration of the planar chiral complex 14b was determined from the anomalous X‐ray dispersion of the crystals of 14b.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Spectroscopic Comparison of Dinuclear Ti+ and Ti2+ μ‐η1:η1 Dinitrogen Complexes with Cp*/Pentafulvene and Amine/Amide Ligation: Moderate versus Strong Activation of N2
Authors: Studt Felix , Lehnert Nicolai , Wiesler Beatrix E. , Scherer Axel , Beckhaus Rüdiger , Tuczek Felix 
Published: November 2005

AbstractThe two dinuclear, end‐on dinitrogen‐bridged titanium complexes with cp*/pentafulvene ligation, [{(η5‐C5Me5)Ti(η6‐C5H4CR2)}2(μ‐η1:η1‐N2)], R = p‐tolyl (1) and >CR2 = adamantylidene (2), are compared to an analogous titanium dinitrogen complex with a mixed amine/amide/chloride ligand set, [{(Me3Si)2NTiCl(TMEDA)}2(μ‐η1:η1‐N2)] (3; TMEDA = tetramethylethylenediamine). The N–N stretching vibrations of complexes 1 and 2 are observed at 1749 and 1755 cm–1, respectively, indicative of a moderate activation of the dinitrogen ligand. In contrast, the N–N stretch of 3 is located at 1284 cm–1, reflecting a much more highly activated N2 ligand. These findings are in qualitative agreement with N–N bond lengths that have been observed experimentally. DFT calculations reveal that the major difference in the electronic structures of 1, 2, and 3 is the fact that only one of the N2 π* orbitals is (doubly) occupied in the case of 1 and 2, whereas both π* orbitals are (doubly) occupied in the case of 3. The reason for this finding is that in 1 and 2 two of the three electrons of each Ti+ are involved in back‐bonding interactions with the terminal fulvene ligands, whereas no such interactions exist between the Ti2+ centers of 3 and its terminal set of donor ligands. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Reaction of the Heteronuclear Cluster [Cp*IrRu3(μ‐H)2(CO)10] with Alkynes: Stereoselective Binding
Authors: Srinivasan Padmamalini , Leong Weng Kee 
Published: November 2005

AbstractThe reaction of the heteronuclear cluster [Cp*IrRu3(μ‐H)2(CO)10] (1) with the symmetrical alkynes RCCR (R = Ph, Et) afforded the butterfly clusters [Cp*IrRu3(CO)9(RCCR)] (2) and the trinuclear clusters [Cp*IrRu2(CO)7(RCCR)] (3) and [Ru3(CO)8(C4R4)] (4). The clusters 2 and 3 have the alkyne aligned parallel to an Ru–Ir bond. The reaction of 1 with unsymmetrical alkynes also afforded stereoselective binding of the alkyne such that the bulkier substituent was pointing away from the Cp*Ir moiety; with PhCCH, however, all three stereoisomers were obtained. With the bis‐silylated alkynes (R = SiMe3, SiEt3), loss of one trialkylsilyl group occurred to give [Cp*IrRu3(CO)9(HCCR)] and [Ru3(CO)9(μ‐H)(CCR)] (5). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Water‐Soluble Arene Ruthenium Complexes Containing a trans‐1,2‐Diaminocyclohexane Ligand as Enantioselective Transfer Hydrogenation Catalysts in Aqueous Solution (Eur. J. Inorg. Chem. 22/2005)
Authors: Canivet Jérôme , Labat Gael , Stoeckli‐Evans Helen , Süss‐Fink Georg 
Published: November 2005

AbstractThe cover picture shows the postulated catalytic cycle for the pH‐dependent, enantioselective transfer hydrogenation of acetophenone to give phenylethanol in water, using formate as hydrogen donor and (arene)ruthenium(trans‐diaminocyclohexane) as chiral catalyst. This work illustrates the increasing interest for water‐soluble enantioselective catalysts operating in aqueous solution. Details are discussed in the article by G. Süss‐Fink et al. on p. 4493 ff.
The Application of [γ‐(Silyloxy)allylidene]ditin to the Efficient Synthesis of the Chromophore of the Neocarzinostatin Dihydroxycyclopentene‐Based Dienediyne Core
Authors: Madec David , Férézou Jean‐Pierre 
Published: November 2005

Abstract1‐(tert‐Butyldimethylsilyl)oxy‐3,3‐bis(tributylstannyl)propene (5), a versatile gem‐dimetallic allylic synthon accessible through various synthetic routes, has been condensed with (trimethylsilyl)propiolaldehyde to give the fully functionalised acyclic vinyltin compound 9h, which is a precursor of the complex dihydroxycyclopentene sub‐unit of neocarzinostatin chromophore (NCS) 1. Subsequent transformation into the geminal (E)‐α‐chloro‐(Z)‐α‐iodovinylic intermediate 20, followed by a palladium‐catalysed carbometallation/cyclisation reaction including in situ trapping with either (tributylstannyl)acetylene or the more functionalised 3,3‐diethoxy‐1‐(tributylstannyl)prop‐1‐yne delivered the corresponding alkyne‐substituted 4‐chloro‐1,2‐bis(silyloxy)cyclopent‐3‐enes 21 or 22, respectively. Chlorocyclopentene 21 was subsequently easily transformed into the target dienediyne adduct 23 by Sonogashira condensation with trimethylsilylacetylene. This diastereoselective process is efficient with only six steps and an overall 26 % yield from the allylic ditin precursor 5. More than just an NCS building block, the final acyclic dihydroxycyclopentene‐based dienediyne is also a seco analogue of the NCS chromophore. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Association of Fluorous “Phase‐Vanishing” Method with Visible‐Light Activation in Benzylic Bromination by Bromine
Authors: Podgoršek Ajda , Stavber Stojan , Zupan Marko , Iskra Jernej 
Published: November 2005

AbstractIn this study the “phase‐vanishing” method for diffusion‐controlled addition of a reagent (Br2) to a reaction phase via a fluorous membrane (C8F18) is combined with an additional mode of activation (visible‐light) to achieve the benzyl bromination of various alkyl‐substituted aromatic compounds in a concentrated solution. Benzyl bromination of p‐tert‐butyltoluene proceeded in various solvents including hexane and methanol, while the reaction of the neat substrate showed a similar selectivity as in carbon tetrachloride. The effect of the substituent on the para position of toluene on the course of bromination revealed three processes: benzyl bromination with H, Me, tBu and CO2Et substituents, aromatic bromination with OMe and NHAc substituents and the reaction of the 4‐acetyl derivative at the substituent to form an α‐bromo ketone.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Sequence‐Selective Peptide Recognition with Designed Modules
Authors: Wehner Mark , Janssen Dominic , Schäfer Gerhard , Schrader Thomas 
Published: November 2005

AbstractA concept for the rational design of sequence‐selective peptide receptors has been extended: in addition to recognition modules for polar, aromatic and basic amino acids, the series has now been completed with new receptor units for apolar and acidic amino acids. The underlying strategy uses the intermolecular β‐sheet stabilization of a dipeptide as a prerequisite to bind its N‐terminal amino acid side chain through a strategically placed recognition tip at the end of a U‐turn protruding from the receptor moiety. Thus, a diaminopyrazole has been covalently attached to Kemp’s triacid by way of a cyclic imide, while a meta‐substituted aniline was coupled as an amide to the pendant third carboxylate arm, bringing the two aromatic units into a sub‐van der Waals distance in a tight conformational lock. NMR titrations, Karplus analyses and Monte‐Carlo simulations demonstrate the effective sequence‐selective recognition of alanine‐containing dipeptides. No example of such a rationally designed set of peptide receptors had existed previously. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Synthesis of Substituted Imidazolo[1,2‐a]piperidinoses and Their Evaluation as Glycosidase Inhibitors
Authors: Dubost Estelle , Le Nouën Didier , Streith Jacques , Tarnus Céline , Tschamber Théophile 
Published: November 2005

AbstractThe synthesis of substituted imidazolo[1,2‐a]‐L‐arabino‐piperidinoses is reported. The substituents are methyl, phenylmethyl, phenylethyl, cyclohexylethyl, pyridinylethyl, piperidinylethyl, phenylpropyl and hydroxymethyl. All substituents are connected to the imidazole moiety. Examination of the inhibitory properties of the newly synthesised compounds against a β‐glucosidase (from almonds) and a β‐galactosidase (from Escherichia coli) lead to the conclusion that the substitution of the C‐2 position on the imidazole moiety with cyclohexylethyl or phenylethyl gives the best results (Ki = 2 and 4 nM, respectively, against a β‐galactosidase) as compared with the non‐substituted azasugar. The synthesis of the imidazolo[1,2‐a]‐D‐xylo‐piperidinose substituted with phenylethyl is also reported, as well as its inhibitory potency against the β‐xylosidase from Aspergillus niger.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
The Synthesis and Structure of Linear and Dendritic Thiourea‐Linked Glycooligomers
Authors: Jiménez Blanco José L. , Bootello Purificación , Ortiz Mellet Carmen , García Fernández José M. 
Published: November 2005

AbstractAn efficient strategy to produce unnatural glycooligomers containing thiourea intersaccharide bridges has been developed. The presence of the thiourea groups in these oligomers should promote the association with polyphosphates, including nucleic acids, due to the hydrogen‐bonding capabilities of the thioureas. Moreover, glycooligomers built from thiourea groups should form complex secondary and tertiary structures due to the interplay of hydrogen bonding and rotational restriction at the bonds adjacent to thiocarbonyl groups. Herein, the preparation and conformational properties of both linear and dendritic architectures are described. This synthetic method relies on the coupling of peracetylated azidoglycosyl isothiocyanates and fully unprotected amine‐functionalised growing oligomers. Deacetylation of the hemiacetylated thiourea adduct and reduction of the azido groups allow entry into a new coupling cycle. The procedure is quite general, should be easily extended to molecular diversity‐oriented and solid‐phase approaches and will allow the investigation of intermolecular interactions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Preparation of 2‐Amino‐4H‐chromene Derivatives from Coumarins in Basic Media
Authors: Curini Massimo , Rosati Ornelio , Marcotullio Maria Carla , Montanari Francesca , Campagna Valerio , Pace Vittorio , Cravotto Giancarlo 
Published: November 2005

AbstractThe reaction of coumarin with cyanoacetate derivatives in the presence of a nucleophilic base (alkoxides or piperidine) follows an interesting pathway that involves both a coumarin skeletal rearrangement and a Michael addition, via a coumaric acid derivative, to afford a substituted 4H‐chromene skeleton. The particular behavior of this process influences the performance and the type of compounds that can be obtained. We demonstrate that the use of an excess of cyanoacetate affords the 4H‐chromene derivative in high yield. An explanation of the mechanism involved in this process is proposed.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Synthesis of Bridged Azabicycles from Pyridines and Pyrrole by a Diallylboration – Ring Closing Metathesis Sequence
Authors: Kuznetsov Nikolai Yu. , Khrustalev Viktor N. , Godovikov Ivan A. , Bubnov Yuri N. 
Published: November 2005

AbstractA straightforward method for the preparation of bridged azabicycles by a diallylboration–ring closing metathesis (RCM) sequence was elaborated. The precursors for the metathesis reaction were prepared by reductive trans‐diallylation of aromatic heterocycles such as pyridines, isoquinoline and pyrrole with triallylborane and an alcohol. Heating of the trans isomers with one equivalent of triallylborane allowed the corresponding cis isomers – or (in the case of pyrrole) a mixture of cis and trans isomers – to be obtained. Boc protection of the amine function gave the precursor for the RCM reaction with axial orientations of allylic groups. The chemical yields of this stage are very good and the amounts of Grubbs’ catalyst required for the reaction do not exceed 2.5 mol‐% (first generation cat.) or 3.7 mol‐% (second generation cat.). Azabicyclo[4.2.1]nonene, obtained from pyrrole, is a key structural motif of the toxin pinnamine. The structures of cis‐1,3‐diallyl‐1,2,3,4‐tetrahydroisoquinoline and azabicyclo[4.3.1]decadiene were studied by single‐crystal X‐ray analysis. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Silylated Vinyloxiranes – Recent Advances and Synthetic Applications
Authors: Marion Frédéric , Calvet Sandrine , Marié Jean‐Charles , Courillon Christine , Malacria Max 
Published: November 2005

AbstractStereoselective preparation of α‐silylated α‐quaternary unsaturated aldehydes 2 from variously substituted silylated vinyloxiranes is achieved with the aid of palladium(0) catalysis under smooth experimental conditions. One example of a versatile application of this rearrangement reaction, in the case of the tert‐butyldimethyl(3‐vinyloxiran‐2‐yl)silane derivative 1a, has resulted in one‐pot diastereoselective syntheses of the highly functionalized polysubstituted δ‐lactones 33–39, the reactivity of which has been studied.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)