all reactions were carried out 
 under a nitrogen atmosphere in oven- or flame - dried glassware . all 
 catalysts and reagents were obtained from commercial sources and were 
 used without further purification with the exception of bf3oet2 , which was purified by distillation from cah2 . n - allyl-4-methylaniline , 2-allyl-4-methylaniline , 2-allylaniline , 2-bromocyclohex-1-ene-1-carbaldehyde , and 2-(but-3-en-2-yl)aniline were prepared according to published procedures . structural and stereochemical assignments were made on the basis of 
 2-d cosy , hsqc , and noesy experiments . ratios of diastereomers were 
 determined by h nmr analysis . high resolution esi mass 
 spectra were acquired using an instrument equipped with at tof mass 
 analyzer , and high resolution ei mass spectra were acquired using 
 an instrument equipped with a magnetic sector mass analyzer . yields 
 refer to isolated yields of compounds estimated to be 95% 
 pure as determined by h nmr analysis unless otherwise 
 noted . the yields reported in the supporting information describe the result of a single experiment , whereas the yields reported 
 in scheme 2 and table 1 are average yields of two or more experiments . thus , the yields 
 reported in the supporting information may 
 differ from those shown in scheme 2 and table 1 . a thick - walled 
 glass pressure 
 tube equipped with a stir bar was sealed with a septum . the pressure 
 tube was flame - dried and cooled under a vacuum and then purged with 
 nitrogen . the flask was charged with n - allyl-4-methoxyaniline 
 ( 2.5 g , 15.2 mmol ) and xylenes ( 30.5 ml ) . the solution was cooled 
 to 0 c , bf3oet2 was added dropwise , 
 and the resulting solution was then allowed to warm to room temperature . the septum was removed , the pressure tube was replaced with a teflon 
 screw cap , the tube was immersed in a 170 c oil bath , and the 
 reaction mixture was allowed to stir for 2 h. the mixture was then 
 cooled to room temperature , and 1 m naoh ( 15 ml ) was added . the resulting 
 mixture was transferred to a separatory funnel , the layers were separated , 
 and the aqueous layer was extracted with dichloromethane ( 3  
 15 ml ) . the combined organic layers were dried over anhydrous na2so4 , filtered , and then concentrated in vacuo . the crude 
 product was purified via flash chromatography on silica gel using 
 5% ethyl acetate : hexanes as the eluent to afford 870 mg ( 35% ) of the 
 title compound as an orange oil : h nmr ( 700 mhz , cdcl3 ) 6.666.62 ( m , 3 h ) , 5.975.91 ( m , 1 h ) , 5.135.08 
 ( m , 2 h ) , 3.74 ( s , 3 h ) , 3.40 ( s , br , 2 h ) , 3.28 ( d , j = 5.6 hz , 2 h ) ; c nmr ( 175 mhz , cdcl3 ) 152.9 , 
 138.3 , 135.7 , 125.7 , 116.9 , 116.2 , 116.0 , 112.7 , 55.7 , 36.6 ; ir ( film ) 
 3357 , 1500 cm ; ms ( esi+ ) 164.1071 ( 164.1070 calcd 
 for c10h13no , m + h ) . a flame - dried flask equipped a stir 
 bar was cooled under a vacuum 
 and then purged with nitrogen . this flask was charged with 2-iodonitrobenzene 
 ( 3.6 g , 14.5 mmol ) and thf ( 58 ml ) . the resulting solution was cooled 
 to 40 c in a mecn / co2(s ) bath , and then a 
 solution of phmgbr ( 16 ml , 16.00 mmol , 1 m in thf ) was added dropwise . the resulting mixture was stirred at 40 c for 5 min , 
 and then a solution of cucn2licl ( 29 ml , 29 mmol , 1 m in thf ) 
 was added dropwise . the reaction mixture was stirred at 40 
 c for 10 min , and then 2-methylallyl bromide ( 2.4 g , 17.5 mmol ) 
 was added dropwise . the mixture was stirred at 40 c 
 for 1 h , and then the reaction was quenched with nh4cl 
 ( 50 ml ) and transferred to a separatory funnel . water ( 50 ml ) was 
 added , the layers were separated , and the aqueous layer was extracted 
 with etoac ( 2  50 ml ) . the organic layers were then combined , 
 washed with brine , dried over anhydrous na2so4 , filtered , and concentrated in vacuo . the crude product was purified 
 via flash chromatography on silica gel using 5% ethyl acetate : hexanes 
 as the eluent to yield slightly impure 2-(2-methylallyl)nitrobenzene 
 ( 1.8 g , 70% yield ) , which was carried on to the next step without 
 further purification . a flame - dried flask equipped with a stir 
 bar was cooled under a vacuum , purged with nitrogen , and charged with 
 2-(2-methylallyl)nitrobenzene ( 1.8 g , 10 mmol ) and etoh ( 67 ml ) . the 
 resulting mixture was stirred at rt until the 2-(2-methylallyl)nitrobenzene 
 was completely dissolved , then powdered zinc ( 9.9 g , 151 mmol ) and 
 acoh ( 8.6 ml , 151 mmol ) were added . the resulting mixture solution 
 was stirred at rt for 1 h and then was filtered through celite , and 
 the celite was washed with et2o . the crude product was purified 
 via flash chromatography on silica gel using 25% ethyl acetate : hexanes 
 as the eluent to afford 1.16 g ( 54% ) of the title compound as a yellow 
 oil that contained ca . data are 
 for the major product : h nmr ( 400 mhz , cdcl3 ) 7.097.02 ( m , 2 h ) , 6.74 ( t , j = 7.6 hz , 
 1 h ) , 6.67 ( d , j = 7.6 hz , 1 h ) , 4.87 ( s , 1 h ) , 4.74 
 ( s , 1 h ) , 3.68 ( s , br , 2 h ) , 3.28 ( s , 2 h ) , 1.73 ( s , 3 h ) ; c nmr ( 100 mhz , cdcl3 ) 145.2 , 143.6 , 131.0 , 127.5 , 123.9 , 
 118.7 , 115.9 , 111.6 , 41.1 , 22.3 ; ir ( film ) 3394 , 1480 cm ; ms ( esi+ ) 148.1125 ( 148.1121 calcd for c10h13n , m + h ) . a flame - dried 
 flask equipped with a stir bar and a reflux condenser the flask was charged 
 with the appropriate 2-allylaniline derivative ( 1.25 equiv ) , the appropriate 
 2-bromobenzaldehyde derivative ( 1.0 equiv ) , 4  molecular sieves 
 ( 1 g / mmol ) , and toluene ( 0.2 m ) . the resulting solution was heated 
 to reflux with stirring overnight . the mixture was then cooled to 
 rt and filtered , and the solids were washed with etoac . the combined 
 organic solutions were then concentrated in vacuo , and the resulting 
 crude imine was immediately used without further purification . a flame - dried flask with a stir bar was cooled under a vacuum and 
 then purged with nitrogen . the flask was charged with the crude imine 
 ( 1 equiv ) and et2o ( 0.5 m ) and was cooled to 0 c . a solution of lialh4 ( 2 equiv , 4 m in et2o ) 
 was added dropwise , and the resulting solution was allowed to warm 
 to rt and stir overnight . the mixture was diluted with et2o , and then water ( 0.1 ml / mmol of lah ) was carefully added dropwise 
 to the solution followed by dropwise addition of 1 m naoh ( 0.1 ml / mmol 
 of lah ) . additional water was then added dropwise until a white solid 
 precipitated and clung to the walls of the flask . the solution was 
 filtered , the flask was washed with et2o , and the resulting 
 solution was also filtered . the combined organic solutions were then 
 concentrated in vacuo , and the crude product was then purified via 
 flash chromatography on silica gel using 25% ethyl acetate : hexanes 
 as the eluent . the coupling of 2-allylaniline ( 894 mg , 
 6.72 mmol ) with 
 2-bromobenzaldehyde ( 994 mg , 5.37 mmol ) was accomplished according 
 to general procedure a. this procedure afforded 1.01 g ( 62% ) of the 
 title compound as a white solid : mp 4244 c ; h nmr ( 400 mhz , cdcl3 )  7.62 ( d , j = 8 hz , 1 h ) , 7.39 ( d , j = 7.6 hz , 1 h ) , 7.267.22 
 ( m , 1 h ) , 7.147.06 ( m , 3 h ) , 6.71 ( t , j = 
 7.2 hz , 1 h ) , 6.53 ( d , j = 8 hz , 1 h ) , 6.035.93 
 ( m , 1 h ) , 5.165.09 ( m , 2 h ) , 4.43 ( s , 2 h ) , 4.27 ( s , br , 1 
 h ) , 3.35 ( d , j = 6 hz , 2 h ) ; c nmr ( 175 
 mhz , cdcl3 ) 145.7 , 138.2 , 136.0 , 132.8 , 129.9 , 129.0 , 128.6 , 
 127.7 , 127.5 , 123.6 , 123.2 , 117.6 , 116.4 , 110.9 , 48.2 , 36.6 ; ir ( film ) 
 3440 , 1512 cm ; ms ( esi+ ) 302.0544 ( 302.0539 calcd 
 for c16h16brn , m + h ) . the coupling of 2-allyl-4-methoxyaniline 
 ( 1.22 g , 7.47 mmol ) with 2-bromobenzaldehyde ( 1.10 g , 5.97 mmol ) was 
 conducted according to general procedure a. this procedure afforded 
 1.09 g ( 55% ) of the title compound as an orange oil : h 
 nmr ( 400 mhz , cdcl3 ) 7.56 ( d , j = 8 hz , 
 1 h ) , 7.34 ( d , j = 7.2 hz , 1 h ) , 7.267.23 
 ( m , 1 h ) , 7.12 ( t , j = 8 hz , 1 h ) , 6.726.63 
 ( m , 2 h ) , 6.49 ( d , j = 8.8 hz , 1 h ) , 6.025.92 
 ( m , 1 h ) , 5.155.09 ( m , 2 h ) , 4.38 ( s , 2 h ) , 3.97 ( s , br , 1 
 h ) , 3.74 ( s , 3 h ) , 3.33 ( d , j = 6 hz , 2 h ) ; c nmr ( 175 mhz , cdcl3 ) 152.1 , 139.8 , 138.5 , 135.7 , 
 132.7 , 129.1 , 128.5 , 127.5 , 125.7 , 123.3 , 116.6 , 116.6 , 112.2 , 112.1 , 
 55.7 , 49.0 , 36.5 ; ir ( film ) 3428 , 1508 cm ; ms 
 ( esi+ ) 332.0645 ( 332.0645 calcd for c17h18brno , 
 m + h ) . the coupling of 2-allyl-4-methylaniline 
 ( 2.20 
 g , 15.0 mmol ) with 2-bromobenzaldehyde ( 2.21 g , 12.0 mmol ) was conducted 
 according to general procedure a. this procedure afforded 2.07 g ( 55% ) 
 of the title compound as an orange oil : h nmr ( 400 mhz , 
 cdcl3 ) 7.56 ( d , j = 8 hz , 1 h ) , 7.34 ( d , j = 7.6 hz , 1 h ) , 7.257.21 ( m , 1 h ) , 7.11 ( t , j = 7.2 hz , 1 h ) , 6.916.89 ( m , 2 h ) , 6.44 ( d , j = 8.8 hz , 1 h ) , 6.035.93 ( m , 1 h ) , 5.145.09 
 ( m , 2 h ) , 4.40 ( s , 2 h ) , 4.14 ( s , br , 1 h ) , 3.32 ( d , j = 6.4 hz , 2 h ) , 2.23 ( s , 3 h ) ; c nmr ( 175 mhz , cdcl3 ) 143.4 , 138.4 , 136.1 , 132.7 , 130.7 , 129.0 , 128.5 , 128.0 , 
 127.5 , 126.7 , 123.8 , 123.3 , 116.3 , 111.1 , 48.5 , 36.6 , 20.4 ; ir ( film ) 
 3437 , 1513 cm ; ms ( esi+ ) 316.0695 ( 316.0695 calcd 
 for c17h18brn , m + h ) . the coupling of 2-allylaniline ( 832 mg , 
 6.25 mmol ) with 2-bromocyclohex-1-ene-1-carbaldehyde ( 945 mg , 5.00 
 mmol ) was conducted according to general procedure a. this procedure 
 afforded 989 mg ( 65% ) of the title compound as a yellow oil that contained 
 ca . data are for the major product : h nmr ( 400 mhz , cdcl3 ) 7.15 ( t , j = 8 hz , 1 h ) , 7.04 ( d , j = 6.8 hz , 1 h ) , 6.70 ( t , j = 8 hz , 1 h ) , 6.64 ( d , j = 8 hz , 1 h ) , 
 6.005.90 ( m , 1 h ) , 5.145.08 ( m , 2 h ) , 4.123.91 
 ( m , 3h ) , 3.29 ( d , j = 6.4 hz , 2 h ) , 2.602.50 
 ( m , 2 h ) , 2.182.09 ( m , 2 h ) , 1.711.60 ( m , 4 h ) ; c nmr ( 175 mhz , cdcl3 ) 146.2 , 136.1 , 133.9 , 129.8 , 
 127.8 , 123.6 , 121.3 , 117.3 , 116.3 , 110.8 , 49.4 , 36.8 , 36.6 , 29.3 , 
 24.7 , 22.4 ; ir ( film ) 3438 , 1508 cm ; ms ( esi+ ) 
 306.0852 ( 306.0852 calcd for c16h20brn , m + 
 h ) . the coupling of 2-allylaniline ( 1.66 g , 
 12.5 
 mmol ) with 2-bromo-5-fluorobenzaldehyde ( 2.02 g , 10.0 mmol ) was conducted 
 according to general procedure a. this procedure afforded 2.28 g ( 72% ) 
 of the title compound as a pale yellow solid : mp 4647 c ; h nmr ( 700 mhz , cdcl3 ) 7.49 ( dd , j = 4.9 , 8.4 hz , 1 h ) , 7.107.06 ( m , 3 h ) , 6.83 ( t , j = 7.7 hz , 1 h ) , 6.72 ( t , j = 7 hz , 1 
 h ) , 6.43 ( d , j = 7.7 hz , 1 h ) , 6.025.96 ( m , 
 1 h ) , 5.175.12 ( m , 2 h ) , 4.38 ( s , 2 h ) , 4.30 ( s , br , 1 h ) , 
 3.37 ( d , j = 4.9 , 2 h ) ; c nmr ( 175 mhz , 
 cdcl3 ) 162.4 ( d , j = 245.3 hz ) , 145.3 , 
 140.8 ( d , j = 6.8 hz ) , 136.0 , 133.9 ( d , j = 7.3 hz ) , 130.1 , 127.8 , 123.7 , 117.9 , 116.8 ( d , j = 2.6 hz ) , 116.5 , 115.9 ( d , j = 23.8 hz ) , 115.6 
 ( d , j = 22.9 hz ) , 110.8 , 48.1 , 36.6 ; ir ( film ) 3440 , 
 1463 cm ; ms ( esi+ ) 320.0450 ( 320.0445 calcd for 
 c16h15brfn , m + h ) . the coupling 
 of 2-allylaniline ( 1.66 g , 12.5 mmol ) with 6-bromo-1,3-benzodioxole-5-carboxaldehyde 
 ( 2.29 g , 10.0 mmol ) was conducted according to general procedure a. 
 this procedure afforded 2.51 g ( 73% ) of the title compound as a white 
 solid : mp 5355 c ; h nmr ( 400 mhz , cdcl3 ) 7.137.06 ( m , 2 h ) , 7.02 ( s , 1 h ) , 6.85 ( s , 1 h ) , 
 6.71 ( t , j = 7.6 hz , 1 h ) , 6.51 ( d , j = 8.4 hz , 1 h ) , 6.035.94 ( m , 3 h ) , 5.165.09 ( m , 
 2 h ) , 4.31 ( d , j = 5.6 hz , 2 h ) , 4.22 ( s , br , 1 h ) , 
 3.34 ( d , j = 6 hz , 2 h ) ; c nmr ( 175 
 mhz , cdcl3 ) 147.6 , 147.4 , 145.6 , 136.0 , 131.6 , 129.9 , 127.7 , 
 123.7 , 117.6 , 116.4 , 113.3 , 112.8 , 110.9 , 109.0 , 101.6 , 48.1 , 36.5 ; 
 ir ( film ) 3439 , 1478 cm ; ms ( esi+ ) 346.0440 ( 346.0437 
 calcd for c17h16brno2 , m + h ) . the coupling of 2-allylaniline ( 1.7 g , 
 12.5 mmol ) with 1-bromo-2-naphthaldehyde ( 2.35 g , 10.00 mmol ) was 
 conducted according to general procedure a except after addition of 
 lialh4 the reaction mixture was heated to reflux overnight . this procedure afforded 2.77 g ( 79% ) of the title compound as an orange 
 solid : mp 9597 c ; h nmr ( 400 mhz , cdcl3 ) 8.34 ( d , j = 8.4 hz , 1 h ) , 7.80 ( d , j = 8 hz , 1 h ) , 7.74 ( d , j = 8.8 hz , 1 
 h ) , 7.60 ( t , j = 7.2 hz , 1 h ) , 7.527.48 ( m , 
 2 h ) , 7.107.06 ( m , 2 h ) , 6.71 ( t , j = 7.2 
 hz , 1 h ) , 6.55 ( d , j = 8.8 hz , 1 h ) , 6.055.95 
 ( m , 1 h ) , 5.165.11 ( m , 2 h ) , 4.66 ( s , 2 h ) , 4.39 ( s , br , 1 
 h ) , 3.37 ( d , j = 6.0 hz , 2 h ) ; c nmr 
 ( 175 mhz , cdcl3 ) 145.8 , 136.6 , 136.0 , 133.9 , 132.4 , 130.0 , 
 128.1 , 127.8 , 127.8 , 127.4 , 126.9 , 126.3 , 126.1 , 123.7 , 123.0 , 117.6 , 
 116.5 , 111.0 , 49.2 , 36.6 ; ir ( film ) 3442 , 1541 cm ; ms ( esi+ ) 352.0700 ( 352.0695 calcd for c20h18brn , m + h ) . the coupling of 2-(2-methylallyl)aniline 
 ( 1.16 g , 7.84 mmol ) with 2-bromobenzaldehyde ( 1.16 g , 6.28 mmol ) was 
 conducted according to general procedure a. this procedure afforded 
 767 mg ( 39% ) of the title compound as a white solid : mp 4346 
 c ; h nmr ( 400 mhz , cdcl3 ) 7.56 ( d , j = 8 hz , 1 h ) , 7.32 ( d , j = 6 hz , 1 h ) , 
 7.257.21 ( m , 1 h ) , 7.147.04 ( m , 3 h ) , 6.70 ( t , j = 7.2 hz , 1 h ) , 6.51 ( d , j = 8 hz , 1 
 h ) , 4.88 ( s , 1 h ) , 4.76 ( s , 1 h ) , 4.424.39 ( m , 3 h ) , 3.33 
 ( s , 2 h ) , 1.73 ( s , 3 h ) ; c nmr ( 175 mhz , cdcl3 ) 146.1 , 143.7 , 138.3 , 132.7 , 130.8 , 128.8 , 128.5 , 127.7 , 127.5 , 
 123.5 , 123.2 , 117.4 , 112.0 , 110.9 , 48.1 , 41.4 , 22.3 ; ir ( film ) 3430 , 
 1510 cm ; ms ( esi+ ) 316.0692 ( 316.0695 calcd for 
 c17h18brn , m + h ) . the coupling of 2-(but-3-en-2-yl)aniline 
 ( 298 mg , 2.02 mmol ) with 2-bromobenzaldehyde ( 300 mg , 1.62 mmol ) was 
 conducted according to general procedure a. this reaction afforded 
 451 mg ( 88% ) of the title compound as a yellow oil that contained 
 ca . data are for the major 
 product : h nmr ( 400 mhz , cdcl3 ) 7.57 ( d , j = 8 hz , 1 h ) , 7.34 ( d , j = 7.6 hz , 1 
 h ) , 7.247.22 ( m , 1 h ) , 7.157.07 ( m , 3 h ) , 6.75 ( t , j = 8 hz , 1 h ) , 6.54 ( d , j = 8 hz , 1 h ) , 
 6.035.94 ( m , 1 h ) , 5.125.07 ( m , 2 h ) , 4.424.37 
 ( m , 3 h ) , 3.52 ( quint , j = 6.4 hz , 1 h ) , 1.43 ( d , j = 7.2 hz , 3 h ) ; c nmr ( 175 mhz , cdcl3 ) 145.2 , 142.3 , 138.3 , 132.8 , 129.0 , 128.6 , 128.5 , 127.5 , 
 127.4 , 126.9 , 123.3 , 117.7 , 114.2 , 111.1 , 48.3 , 38.1 , 18.9 ; ir ( film ) 
 3434 , 1506 cm ; ms ( esi+ ) 316.0693 ( 316.0695 calcd 
 for c17h18brn , m + h ) . the coupling of 2-allylaniline ( 1.66 g , 12.5 
 mmol ) with 2-bromoacetophenone ( 2.00 g , 10.0 mmol ) was conducted 
 according to general procedure a except after addition of lialh4 the reaction mixture was heated to reflux overnight . this 
 procedure afforded 1.75 g ( 55% ) of the title compound as a yellow 
 oil that contained ca . 6% of an unknown impurity : h nmr 
 ( 400 mhz , cdcl3 ) 7.54 ( d , j = 8 hz , 1 
 h ) , 7.37 ( d , j = 7.6 hz , 1 h ) , 7.19 ( t , j = 7.2 hz , 1 h ) , 7.087.02 ( m , 2 h ) , 6.97 ( t , j = 8 hz , 1 h ) , 6.63 ( t , j = 7.6 hz , 1 h ) , 6.18 ( d , j = 8 hz , 1 h ) , 6.075.97 ( m , 1 h ) , 5.235.18 
 ( m , 2 h ) , 4.84 ( quint , j = 6.4 hz , 1 h ) , 4.25 ( s , 
 br , 1 h ) , 3.40 ( d , j = 6 hz , 2 h ) , 1.48 ( d , j = 6.4 hz , 3 h ) ; c nmr ( 175 mhz , cdcl3 ) 144.7 , 143.6 , 136.3 , 132.9 , 129.7 , 128.3 , 128.0 , 127.6 , 
 126.7 , 122.9 , 122.6 , 117.2 , 116.3 , 111.6 , 52.4 , 36.9 , 23.1 ; ir ( film ) 
 3746 , 1506 cm ; ms ( esi+ ) 316.0692 ( 316.0695 calcd 
 for c17h18brn , m + h ) . a flame - dried schlenk tube equipped with a stir 
 bar was cooled under a vacuum and then purged with nitrogen . the tube 
 was charged with naobu ( 96 mg , 1 mmol ) , 
 pd2(dba)3 ( 9 mg , 0.01 mmol ) , and pcy3hbf4 ( 15 mg , 0.040 mmol ) . the substrate ( 0.5 mmol ) 
 was dissolved in toluene ( 5 ml ) and added to the flask . the resulting 
 solution was heated 105 c with stirring for 18 h , at which time 
 the substrate was judged to be completely consumed by gc , tlc , or h nmr analysis of an aliquot removed from the reaction mixture . the mixture was then cooled to rt , and saturated aqueous nh4cl ( 10 ml ) was added . the mixture was transferred to a separatory 
 funnel , the layers were separated , and the aqueous layer was extracted 
 with etoac ( 3  15 ml ) . the combined organic layers were then 
 dried over anhydrous na2so4 , filtered , and concentrated 
 in vacuo . the crude product was then purified via flash chromatography 
 on silica gel using 2% ethyl acetate : hexanes as the eluent to afford 
 a product that still contained small amounts of impurities . the product 
 was then dissolved in 30% et2o / hexanes ( 5 ml , 0.1 m ) and 
 2 m hcl in et2o ( 1.5 ml , 3 equiv ) was added dropwise . the 
 resulting solution was stirred at rt for 1 min , and a white solid 
 ( the product hcl salt ) precipitated from the solution . the salt was then dissolved 
 in dicholoromethane ( 10 ml ) and transferred to a separatory funnel . 
 a solution of 4 m naoh was added , and the mixture was shaken vigorously 
 for 1 min . the layers were then separated , and the aqueous layer was 
 extracted with dichloromethane ( 3  15 ml ) . the combined organic 
 layers were dried over anhydrous na2so4 , filtered , 
 and concentrated in vacuo to afford the desired product . the cyclization of 3a ( 151 
 mg , 0.500 mmol ) was conducted according to general procedure b to 
 afford 94 mg ( 85% ) of the title compound as a yellow solid : mp 125127 
 c ; h nmr ( 400 mhz , cdcl3 ) 7.207.10 
 ( m , 6 h ) , 6.72 ( t , j = 7.2 hz , 1 h ) , 6.55 ( d , j = 8 hz , 1 h ) , 4.58 ( d , j = 15.6 hz , 1 
 h ) , 4.02 ( d , j = 15.2 hz , 1 h ) , 3.583.50 
 ( m , 1 h ) , 3.15 ( dd , j = 7.6 , 15.2 hz , 1 h ) , 3.053.00 
 ( m , 2 h ) , 2.75 ( dd , j = 11.2 , 15.0 hz , 1 h ) ; c nmr ( 175 mhz , cdcl3 ) 151.8 , 134.7 , 133.5 , 129.5 , 
 129.3 , 127.5 , 126.9 , 126.3 , 126.1 , 124.4 , 118.5 , 107.0 , 61.6 , 48.5 , 
 35.7 , 35.6 ; ir ( film ) 2778 , 1456 cm ; ms ( ei ) 221.1201 
 ( 221.1204 calcd for c16h15n , m ) . the cyclization of 3b ( 166 
 mg , 0.500 mmol ) was conducted according to general 
 procedure b except only 1 equiv of 2 m hcl in et2o was 
 used . this procedure afforded 86 mg ( 68% ) of the title compound as 
 a yellow solid : mp 134 c ( dec ) ; h nmr ( 700 mhz , 
 cdcl3 ) 7.197.14 ( m , 4 h ) , 6.80 ( s , 1 h ) , 6.68 ( d , j = 7 hz , 1 h ) , 6.50 ( d , j = 7 hz , 1 h ) , 
 4.54 ( d , j = 14.7 hz , 1 h ) , 3.93 ( d , j = 14.7 hz , 1 h ) , 3.74 ( s , 3 h ) , 3.453.40 ( m , 1 h ) , 3.11 
 ( dd , j = 7.7 , 14.7 hz , 1 h ) , 3.053.02 ( m , 
 2 h ) , 2.73 ( dd . j = 11.9 , 14.7 hz , 1 h ) ; c nmr ( 175 mhz , cdcl3 ) 153.4 , 146.2 , 134.6 , 133.6 , 131.2 , 
 129.3 , 126.9 , 126.3 , 126.0 , 112.2 , 111.6 , 107.3 , 62.6 , 56.0 , 49.6 , 
 36.0 , 35.4 ; ir ( film ) 2781 , 1486 cm ; ms ( ei ) 251.1314 
 ( 251.1310 calcd for c17h17no , was conducted according to general 
 procedure b to afford 98 mg ( 81% ) of the title compound as a brown 
 solid : mp 6870 c ; h nmr ( 400 mhz , cdcl3 ) 7.217.15 ( m , 4 h ) , 6.976.92 ( m , 2 h ) , 6.49 
 ( d , j = 8 hz , 1 h ) , 4.58 ( d , j = 
 15.2 hz , 1 h ) , 3.98 ( d , j = 15.2 hz , 1 h ) , 3.523.44 
 ( m , 1 h ) , 3.11 ( dd , j = 14.8 , 7.6 hz , 1 h ) , 3.043.02 
 ( d , j = 6.8 hz , 2 h ) , 2.74 ( dd , j = 14.8 , 11.2 hz , 1 h ) , 2.27 ( s , 3 h ) ; c nmr ( 175 mhz , 
 cdcl3 ) 149.8 , 134.8 , 133.7 , 129.9 , 129.3 , 128.0 , 127.6 , 
 127.0 , 126.4 , 126.1 , 125.4 , 107.0 , 62.2 , 49.2 , 35.7 , 35.6 , 20.9 ; ir 
 ( film ) 2918 , 1491 cm ; ms ( ei ) 235.1358 ( 235.1361 
 calcd for c17h17n , m ) . the cyclization of 3d ( 153 
 mg , 0.500 mmol ) was conducted according to general procedure b. in 
 order to remove a small amount of unreacted starting material from 
 the product , the crude product was dissolved in dichloromethane ( 2.5 
 ml ) , and dmap ( 6.1 mg , 0.050 mmol ) and et3n ( 104 l , 
 0.750 mmol ) were added to the solution . acetic anhydride ( 61 l , 
 0.650 mmol ) was added , and the solution was allowed to stir at rt 
 for 3 h and was then concentrated in vacuo . the crude product was 
 purified via flash chromatography to afford 62 mg ( 55% ) of the title 
 compound as a brown solid : mp 8890 c ; h 
 nmr ( 700 mhz , cdcl3 ) 7.097.06 ( m , 2 h ) , 6.67 ( t , j = 7.0 hz , 1 h ) , 6.45 ( d , j = 7.7 hz , 
 1 h ) , 3.68 ( d , j = 15.4 hz , 1 h ) , 3.343.29 
 ( m , 1 h ) , 3.18 ( d , j = 15.4 hz , 1 h ) , 3.03 ( dd , j = 7.0 , 14.7 hz , 1 h ) , 2.61 ( t , j = 12.6 
 hz , 1 h ) , 2.21 ( t , j = 14.7 hz , 1 h ) , 2.12 ( d , j = 16.1 hz , 1 h ) , 2.021.91 ( m , 4 h ) , 1.771.71 
 ( m , 2 h ) , 1.571.52 ( m , 2 h ) ; c nmr ( 175 mhz , 
 cdcl3 ) 151.9 , 129.6 , 127.5 , 127.3 , 125.7 , 124.2 , 118.1 , 
 106.8 , 61.5 , 49.6 , 36.5 , 35.8 , 30.2 , 27.7 , 22.9 , 22.8 ; ir ( film ) 2916 , 
 1607 cm ; ms ( ei ) 225.1518 ( 225.1518 calcd for 
 c16h19n , m ) . the cyclization 
 of 3e ( 161 mg , 0.505 mmol ) was conducted according to 
 general 
 procedure b to afford 105 mg ( 87% ) of the title compound as a yellow 
 solid : mp 9293 c ; h nmr ( 400 mhz , cdcl3 ) 7.137.07 ( m , 3 h ) , 6.896.85 ( m , 2 h ) , 6.73 
 ( t , j = 7.2 hz , 1 h ) , 6.54 ( d , j = 8 hz , 1 h ) , 4.54 ( d , j = 15.6 hz , 1 h ) , 3.98 
 ( d , j = 15.6 hz , 1 h ) , 3.553.47 ( m , 1 h ) , 
 3.15 ( dd , j = 4.6 , 14.8 hz , 1 h ) , 3.022.90 
 ( m , 2 h ) , 2.74 ( dd , j = 11.2 , 14.8 hz , 1 h ) ; c nmr ( 175 mhz , cdcl3 ) 161.3 ( d , j = 242.6 hz ) , 151.6 , 135.4 ( d , j = 7 hz ) , 130.7 
 ( d , j = 7.5 hz ) , 130.3 ( d , j = 2.6 
 hz ) , 129.5 , 127.6 , 124.5 , 118.8 , 113.6 ( d , j = 21 
 hz ) , 113.3 ( d , j = 21.7 hz ) , 107.1 , 61.8 , 48.6 ( d , j = 1.9 hz ) , 35.6 , 34.9 ; ir ( film ) 2789 , 1480 cm ; ms ( ei ) 239.1116 ( 239.1110 calcd for c16h14fn , m ) . the cyclization 
 of 3f ( 173 mg , 0.500 mmol ) was conducted according to 
 general procedure b to afford 95 mg ( 72% ) of the title compound as 
 a white solid : mp 9092 c ; h nmr ( 400 mhz , 
 cdcl3 ) 7.127.09 ( m , 2 h ) , 6.72 ( t , j = 7.2 hz , 1 h ) , 6.60 ( d , j = 6.8 hz , 2 h ) , 6.53 
 ( d , j = 8 hz , 1 h ) , 5.88 ( s , 2 h ) , 4.46 ( d , j = 14.8 hz , 1 h ) , 3.92 ( d , j = 14.8 hz , 
 1 h ) , 3.523.43 ( m , 1 h ) , 3.13 ( dd , j = 7.6 , 
 15.0 hz , 1 h ) , 2.90 ( d , j = 7.2 hz , 2 h ) , 2.74 ( dd , j = 10.8 , 15.0 hz , 1 h ) ; c nmr ( 175 mhz , cdcl3 ) 151.6 , 146.1 , 146.1 , 129.4 , 127.6 , 127.4 , 126.2 , 124.3 , 
 118.5 , 108.8 , 106.9 , 106.5 , 100.8 , 61.5 , 48.5 , 35.5 , 35.5 ; ir ( film ) 
 2891 , 1484 cm ; ms ( ei ) 265.1103 ( 265.1103 calcd 
 for c17h15no2 , m ) . the cyclization 
 of 3 g ( 173 mg , 0.491 mmol ) was conducted according to 
 general procedure b to afford 106 mg ( 80% ) of the title compound as 
 a red solid : mp 9597 c ; h nmr ( 400 mhz , 
 cdcl3 ) 7.94 ( d , j = 8.4 hz , 1 h ) , 7.79 
 ( d , j = 8 hz , 1 h ) , 7.66 ( d , j = 
 8.4 hz , 1 h ) , 7.50 ( t , j = 7.2 hz , 1 h ) , 7.44 ( t , j = 6.8 hz , 1 h ) , 7.22 ( d , j = 8.4 hz , 
 1 h ) , 7.167.12 ( m , 2 h ) , 6.75 ( t , j = 7.2 
 hz , 1 h ) , 6.60 ( d , j = 8 hz , 1 h ) , 4.64 ( d , j = 15.6 hz , 1 h ) , 4.12 ( d , j = 15.6 hz , 
 1 h ) , 3.603.51 ( m , 2 h ) , 3.22 ( dd , j = 7.2 , 
 14.8 hz , 1 h ) , 3.09 ( t , j = 12.8 hz , 1 h ) , 2.85 ( dd , j = 11.6 , 14.2 hz , 1 h ) ; c nmr ( 175 mhz , cdcl3 )  151.9 , 132.5 , 132.4 , 130.9 , 129.9 , 129.8 , 128.6 , 
 127.6 , 126.6 , 126.3 , 125.4 , 125.4 , 124.6 , 122.9 , 118.8 , 107.3 , 61.8 , 
 49.3 , 36.1 , 32.0 ; ir ( film ) 2924 , 1482 cm ; ms 
 ( ei ) 271.1351 ( 271.1361 calcd for c20h17n , m ) . the cyclization 
 of 3h ( 163 mg , 0.517 mmol ) was conducted according to 
 general 
 procedure b to afford 97 mg ( 80% ) of the title compound as a yellow 
 solid : mp 4750 c ; h nmr ( 700 mhz , cdcl3 ) 7.197.14 ( m , 3 h ) , 7.06 ( m , 3 h ) , 6.63 ( t , j = 7.0 hz , 1 h ) , 6.41 ( d , j = 7.7 hz , 
 1 h ) , 4.50 ( d , j = 16.1 hz , 1 h ) , 4.25 ( d , j = 16.1 hz , 1 h ) , 3.10 ( d , j = 15.4 hz , 
 1 h ) , 2.94 ( s , 2 h ) , 2.70 ( d , j = 15.4 hz , 1 h ) , 
 1.15 ( s , 3 h ) ; c nmr ( 175 mhz , cdcl3 ) 150.5 , 
 134.6 , 132.9 , 129.8 , 128.3 , 127.6 , 126.5 , 126.4 , 126.0 , 124.8 , 117.2 , 
 106.2 , 62.3 , 43.7 , 43.7 , 40.0 , 20.9 ; ir ( film ) 2924 , 1482 cm ; ms ( ei ) 235.1364 ( 235.1361 calcd for c17h17n , the cyclization 
 of 3i ( 64 mg , 0.202 mmol ) was conducted according to 
 general procedure b to afford 36 mg ( 75% ) of the title compound as 
 a yellow oil . this product was judged to have been formed with 18:1 
 dr by h nmr analysis . data are for the major isomer : h nmr ( 700 mhz , cd3od ) 7.197.15 ( m , 4 h ) , 
 7.097.06 ( m , 2 h ) , 6.76 ( t , j = 7.7 hz , 1 
 h ) , 6.62 ( d , j = 7.7 hz , 1 h ) , 4.58 ( d , j = 15.4 hz , 1 h ) , 3.83 ( d , j = 14.7 hz , 1 h ) , 3.06 
 ( d , j = 14.7 hz , 1 h ) , 2.922.84 ( m , 3 h ) , 
 1.37 ( d , j = 6.3 hz , 3 h ) ; c nmr ( 175 
 mhz , cd3od ) 152.7 , 136.1 , 135.6 , 134.6 , 130.3 , 128.4 , 127.9 , 
 127.4 , 127.1 , 123.5 , 120.3 , 108.7 , 71.5 , 50.3 , 43.3 , 35.0 , 16.1 ; ir 
 ( film ) 3676 , 1506 cm ; ms ( ei ) 235.1363 ( 235.1361 
 calcd for c17h17n , m ) . the cyclization 
 of 3j ( 165 mg , 0.500 mmol ) was conducted according to 
 the general 
 procedure b to afford 64 mg ( 52% ) of the title compound as a yellow 
 oil . 2:1:1 mixture 
 of the two possible diastereomers and a side product tentatively assigned 
 as 6-methyl-11-methylene-5,6,11,12-tetrahydrodibenzo[b , f]azocine , which results from competing intramolecular 
 heck reaction . data are for the mixture : h nmr ( 700 mhz , cdcl3 ) 7.267.24 ( m , 1 h ) , 
 7.227.20 ( m , 1.5 h ) , 7.197.16 ( m , 2.5 h ) , 7.167.14 
 ( m , 2.5 h ) , 7.127.07 ( m , 4.5 h ) , 7.02 ( d , j = 7.7 hz , 1 h ) , 6.97 ( t , j = 10.5 hz , 1 h ) , 6.686.63 
 ( m , 2 h ) , 6.60 ( d , j = 7.7 hz , 0.5 h ) , 6.48 ( d , j = 8.4 hz , 1 h ) , 6.45 ( d , j = 7.7 hz , 
 0.5 hz ) , 6.29 ( ddd , j = 3.5 , 10.5 , 17.3 hz , 0.5 h ) , 
 5.235.13 ( m , 1 h ) , 4.844.78 ( m , 1.5 h ) , 4.534.50 
 ( m , 1 h ) , 3.973.92 ( m , 1 h ) , 3.763.60 ( m , 1 h ) , 3.23 
 ( dd , j = 8.4 , 14.7 hz , 1 h ) , 3.062.92 ( m , 
 4 h ) , 2.772.72 ( m , 1.5 h ) , 1.55 ( d , j = 6.3 
 hz , 1.5 h ) , 1.53 ( d , j = 7.0 hz , 1.5 h ) , 1.36 ( d , j = 7.0 hz , 3 h ) ; c nmr ( 175 mhz , cdcl3 ) 151.3 , 149.8 , 146.0 , 143.5 , 140.9 , 140.4 , 139.8 , 139.2 , 
 134.5 , 134.0 , 132.6 , 130.2 , 129.6 , 129.3 , 129.0 , 128.8 , 127.7 , 127.7 , 
 127.5 , 127.4 , 127.4 , 127.2 , 127.1 , 127.0 , 126.5 , 126.3 , 126.0 , 124.5 , 
 124.2 , 123.5 , 122.3 , 117.9 , 117.8 , 117.5 , 117.3 , 115.3 , 106.9 , 106.3 , 
 62.7 , 56.4 , 54.6 , 53.9 , 50.6 , 48.0 , 36.3 , 36.1 , 35.8 , 35.3 , 24.9 , 
 19.2 , 17.2 ; ir ( film ) 3362 , 1617 cm ; ms ( esi+ ) 
 236.1442 ( 236.1434 calcd for c17h17n , m + h ) .
intramolecular pd - catalyzed alkene 
 carboamination reactions of 
 substituted 2-allyl - n-(2-bromobenzyl)anilines are 
 described . 
 the substrates for these reactions are generated in two 
 steps from readily available 2-allylanilines and 2-bromobenzaldehyde 
 derivatives . 
 the transformations afford substituted tetrahydroindoloisoquinolines , 
 an uncommon class of fused bicyclic heterocycles , in good yield . 
 the 
 mechanism of these transformations is described , and a model that 
 accounts for the observed product stereochemistry is proposed .