gold(i ) 
 complexes are very active and selective catalysts for the 
 addition of nucleophiles on 1,n - enynes .
the most emblematic 
 transformation in this area is the addition of alcohols and water 
 on 1,6-enynes 1 ( alkoxy- or hydroxycyclization ) , which 
 occurs stereospecifically to form adducts 3 in the presence 
 of gold(i ) catalysts under much milder conditions than 
 with other electrophilic metal catalysts ( scheme 1 ) . according to dft calculations
, 
 this reaction proceeds through intermediates 2 , whose 
 structures are intermediate between cyclopropyl gold(i ) carbenes and 
 gold(i)-stabilized homoallyl carbocations .
it is interesting to note that the hydroxycyclization is usually 
 much faster than the direct nucleophilic addition of water on the 
 terminal alkyne to form the corresponding methyl ketone .
enantioselective hydroxy- and alkoxycyclizations 
 of 1,6-enynes have been achieved with moderate to good enantioselectivities 
 with a variety of chiral phosphines or nhc - gold catalysts .
the intermolecular reaction 
 of 1,6-enynes with carbamates roconh2 ( r = et , bn ) and 
 anilines also takes place using ph3paucl and agsbf6 ( 5 mol % ) .
however , in the latter 
 case , only less basic anilines bearing strongly electron - withdrawing 
 groups ( p - no2 , o - cn , o - cf3 , p - cl ) were used as the 
 nucleophiles .
we decided to study the scope and limitations of the 
 intermolecular amination of 1,6-enynes with a broader range of anilines 
 using gold(i ) complexes with johnphos and related bulky biphenyl - based 
 phosphines ( buchwald ligands ) , which are often the catalysts of choice 
 in gold(i)-catalyzed reactions .
the aminocyclization of enynes 
 was initially studied with dimethyl 
 2-trans - cinnamyl-2-(prop-2-yn-1-yl)malonate ( 1a ) as the substrate and a slight excess of the aniline using 
 25 mol % of the gold catalyst in ch2cl2 ( table 1 ) . the best 
 result for the addition of aniline
gold(i ) catalyst a , leading to adduct 4a in excellent yield ( table 1 , entry 1 ) . increasing 
 the catalyst loading to 5 mol %
was required for the addition of p - anisidine to form 4b in 58% yield after a 
 19 h reaction time ( table 1 , entry 2 ) .
this result with an electron - rich aniline is remarkable 
 since this reaction had only been reported with deactivated amines .
lower yields were obtained with gold(i ) complexes 
 with other phosphine , nhc , or phosphite ligands ( table 1 , entries 37 ) .
tetrahydrofuran 
 was also evaluated as solvent in the reaction with aniline ; however , 
 the yield was significantly reduced .
it is important 
 to note that the reaction of anilines and aliphatic 
 amines with complex a forms complexes [ ( johnphos)au(nh2r)]sbf6 by ligand substitution , which have been 
 characterized by x - ray diffraction and show diminished catalytic activity 
 in the reaction of cyclopropenes with p - anisidine .
however , in our system , these less active amino 
 complexes presumably formed in situ under the amination reaction still 
 undergo ligand exchange with the enynes at a sufficient rate so as 
 to generate the catalytically active ( -alkyne)gold(i ) 
 species . the substrate generality 
 under these reaction conditions was tested 
 with different enynes and a wide range of anilines ( table 2 ) .
in general , moderate to excellent 
 yields were obtained for the different combinations of 1,6-enynes 
 and anilines examined ( 4298% ) . concerning the anilines , electron - rich 
 as well as electron - poor anilines participated efficiently in this 
 reaction without significant differences in the isolated yields .
anilines 
 substituted at the ortho - position also gave rise 
 to the corresponding adducts 4c , 4e , 4h , 4o , 4w , and 4y in 
 satisfactory yields .
secondary anilines , such as n - methylaniline , n - allylaniline , indoline , or tetrahydroquinoline 
 also reacted to give the corresponding adducts in moderate to good 
 yields ( 4l , 4 t , 4ad  ag ) .
different substitution patterns on the enyne were also 
 used , and all led efficiently to the desired product .
the presence 
 of a dimethyl or phenyl substituent on the alkene did not give significantly 
 different results in terms of reactivity .
the relative configuration 
 of the aminocyclization products was assigned by determining the structures 
 of compounds 4d , 4i , and 4x by x - ray crystallography analysis , confirming 
 the anti - type addition of the nucleophile to the 
 1,6-enyne . to illustrate the synthetic potential of this gold(i ) 
 catalyzed 
 reaction , additional transformations were carried out on several halogenated 
 derivatives , in order to increase the molecular complexity .
first , 
 an intramolecular heck reaction was successfully applied for compounds 
 bearing iodine in the ortho position ( scheme 2 , 4e 
g ) . under standard conditions , good yields of the desired cis - fused tricyclic structures 5e
the use of o - br derivative 4c or dimethyl 
 substituted compound 4y only led to the recovery of the 
 starting material .
it is interesting to note that the initial alkyl - palladium(ii ) 
 species of the heck reaction evolves by an intramolecular redox process 
 presumably via -hydride elimination from the benzylic position 
 of cationic intermediate int(45 ) , followed by 
 reductive elimination .
then , we envisioned 
 a second gold - catalyzed aminocyclization to 
 form n - substituted indoles ( scheme 2 ) .
the alkyne was introduced at the ortho position by sonogashira cross - coupling of the iodoarenes 
 with trimethylsilylacetylene to form 6e  g in near - quantitative yields , followed by deprotection of 
 the tms - alkynyl compounds by methanolysis to give 7e 
the new gold(i)-catalyzed aminocyclization proceeded efficiently 
 using catalyst d2 with ipr as 
 the nhc ligand , leading to indole derivatives 8e  g in good yields .
the presence of chlorine or bromine atoms 
 in 5f  g and 8f  g could allow their further functionalizations by cross - coupling 
 reactions or other tranformations .
although amines coordinate to lewis acidic gold(i ) complexes , thus 
 reducing their availability to activate alkynes and other substrates , 
 robust cationic gold(i ) complex [ johnphosau(mecn)]sbf6 is the catalyst of choice for the broad - scope aminocyclization of 
 1,6-enynes .
the reaction proceeds under mild conditions in moderate 
 to excellent yields with a wide variety of substituted anilines , including 
 electron - rich as well as secondary n - alkyl anilines 
 to give the corresponding adducts , which can be further derivatized 
 to form polycyclic compounds by palladium- and gold - catalyzed reactions .
solvents were dried 
 by passing through an activated alumina column on a solvent purification 
 system .
analytical thin layer chromatography was carried out using 
 tlc - aluminum sheets with 0.2 mm of silica gel ( merck gf254 ) using 
 uv light as the visualizing agent or an acidic solution of vanillin 
 in ethanol as the developing agent .
purifications by chromatography 
 were carried out using flash grade silica gel ( sds chromatogel 60 
 acc , 4060 mm ) .
preparative tlc was performed on 20 cm  
 20 cm silica gel plates ( 2.0 mm thick , catalogue number 02015 , analtech ) . 

organic solutions were concentrated under reduced pressure on a rotary 
 evaporator . unless otherwise stated ,
nmr spectra were recorded at 
 298 k on 300 , 400 , and 500 mhz devices .
h and c chemical shifts (  ) are given in ppm relative to tms , and 
 coupling constants ( j ) , in hz .
the solvent signals 
 were used as references , and the chemical shifts were converted to 
 the tms scale .
mass spectra were recorded employing tof mass analyzers 
 ( esi , ei , ci ) .
melting points were determined by observation of the 
 fusion of the solids placed in a capillary , through a magnifying glass . 

crystal structure determinations were carried out using a diffractomer 
 equipped with an appex 2 4k ccd area detector , an fr591 rotating anode 
 with mo k radiation , montel mirrors as the monochromator , and 
 a kryoflex low temperature device ( t = 173 
 c ) .
programs used : data collection apex-2 , data reduction bruker saint 
 v/.60a and absorption correction sadabs .
structure solution and refinement : 
 crystal structure solution was achieved using direct methods as implemented 
 in shelxtl and visualized using the program xp .
missing atoms were 
 subsequently located from difference fourier synthesis and added to 
 the atom list .
least - squares refinement on f2 using all measured intensities 
 was carried out using the program shelxtl .
gold complexes a , b , and c are commercialy available ; d1,d2 , and e(2 ) were prepared according to literature 
 procedures .
lialh4 ( 461 mg , 12.1 mmol ) was suspended in anhydrous thf ( 30 ml ) , 
 and the slurry was cooled to 0 c .
a solution of malonate 1a ( 1.58 g , 5.52 mmol ) in anhydrous thf ( 2 ml ) was added dropwise 
 at 0 c .
when effervescence had ceased , the mixture was allowed 
 to warm to room temperature and was then heated at 45 c and 
 stirred vigorously for 3.5 h. tlc ( c - hexane / etoac 8:1 and 1:1 ) showed 
 full consumption of the starting malonate and clean conversion .
the 
 mixture was diluted with wet diethyl ether ( 30 ml ) and quenched by 
 addition of sodium sulfate decahydrate ( ca .
2 g ) slowly , to control 
 the effervescence . after stirring for 1 h at rt ,
a few drops of saturated 
 aqueous nh4cl were added , until the suspension became white . 

the solids were filtered off over celite , and the cake was washed 
 thoroughly with diethyl ether ( 200 ml ) .
the filtrate was concentrated in vacuo , and the residue was purified by column chromatography 
 on silica gel eluting with pentane / diethyl ether 1:1 to straight diethyl 
 ether to afford 1.15 g of a colorless solid ( 90% ) .
h nmr ( 500 mhz , cdcl3 )  7.397.35 
 ( m , 2h ) , 7.347.29 ( m , 2h ) , 7.257.21 ( m , 1h ) , 6.50 
 ( d , j = 15.6 hz , 1h ) , 6.23 ( dt , j = 15.6 , 7.7 hz , 1h ) , 3.763.67 ( m , 4h ) , 2.432.37 
 ( m , 2h ) , 2.33 ( dd , j = 7.7 , 1.4 hz , 2h ) , 2.32 ( d , j = 2.8 hz , 2h ) , 2.08 ( t , j = 2.7 hz , 1h ) 
 ppm .
c nmr ( 126 mhz , cdcl3 )  137.2 , 133.6 , 128.5 , 127.3 , 126.1 , 124.8 , 80.9 , 
 71.0 , 67.5 , 42.7 , 35.2 , 21.6 ppm .
hrms - apci calcd for 
 c15h19o2 [ m + h ] : 231.1380 ; found : 231.1386 .
2-cinnamyl-2-(prop-2-yn-1-yl)propane-1,3-diol 
 ( 600 mg , 2.61 mmol ) was dissolved in anhydrous acetone ( 2 ml ) and ptsohh2o ( 25 mg , 0.13 mmol ) was added , 
 followed by addition of mgso4 ( 300 mg ) .
the suspension 
 was stirred vigorously at rt for 24 h. tlc showed clean conversion 
 to a new product and only traces of starting material .
acetone was 
 removed under a stream of nitrogen , and the mixture was loaded on 
 silica gel and purified by column chromatography eluting with pentane / diethyl 
 ether 95:5 to 9:1 to afford 650 mg of a colorless oil ( 92% ) .
h nmr ( 500 mhz , cdcl3 )  
 7.397.35 ( m , 2h ) , 7.357.30 ( m , 2h ) , 7.267.21 
 ( m , 1h ) , 6.51 ( d , j = 15.8 hz , 1h ) , 6.19 ( dt , j = 15.6 , 7.7 hz , 1h ) , 3.73 ( s , 4h ) , 2.42 ( d , j = 2.8 hz , 2h ) , 2.37 ( dd , j = 7.8 , 1.3 hz , 2h ) , 
 2.08 ( t , j = 2.7 hz , 1h ) , 1.46 ( s , 3h ) , 1.44 ( s , 
 3h ) ppm . c nmr ( 126 mhz , cdcl3 )  137.2 , 133.9 , 128.5 , 127.3 , 126.1 , 124.0 , 98.2 , 
 80.6 , 71.1 , 66.7 , 36.1 , 36.0 , 25.3 , 22.5 , 22.2 ppm .
hrms - esi calcd for c18h22o2na [ m + na ] : 293.1512 ; found : 293.1512 . in a dry 
 flask , 2-cinnamyl-2-(prop-2-yn-1-yl)propane-1,3-diol ( 200 mg , 0.87 
 mmol ) was dissolved in anhydrous thf ( 2 ml ) , and nah ( 80 mg , 2 mmol ) , 
 mei ( 135 ml , 2.17 mmol ) , and tbai ( 48 mg , 0.13 mmol ) were added sequentially . 

the suspension was stirred vigorously at rt for 24 h. tlc showed full 
 consumption of starting material and conversion to diprotected alcohol 
 with traces of monoprotection .
the mixture was quenched by careful 
 addition of saturated aqueous nh4cl ( 30 ml ) and extracted 
 with diethyl ether ( 3  50 ml ) .
the combined organic layers were 
 washed with brine ( 2  15 ml ) , dried over mgso4 , and 
 filtered , and the solvent was removed under vacuum .
the resulting 
 mixture was purified by column chromatography on silica gel eluting 
 with c - hexane / etoac 10:1 to afford 210 mg of a colorless oil ( 94% ) .
h nmr ( 500 mhz , cdcl3 )  7.397.35 ( m , 2h ) , 7.347.29 ( m , 2h ) , 7.257.20 
 ( m , 1h ) , 6.47 ( d , j = 15.8 hz , 1h ) , 6.23 ( dt , j = 15.6 , 7.7 hz , 1h ) , 3.36 ( s , 6h ) , 3.343.28 ( m , 
 4h ) , 2.34 ( dd , j = 7.7 , 1.3 hz , 2h ) , 2.27 ( d , j = 2.7 hz , 2h ) , 2.02 ( t , j = 2.7 hz , 1h ) 
 ppm .
c nmr ( 126 mhz , cdcl3 )  137.7 , 133.1 , 128.5 , 127.0 , 126.1 , 125.7 , 81.3 , 
 74.3 , 70.1 , 59.3 , 42.4 , 35.4 , 22.2 ppm .
hrms - apci calcd 
 for c17h23o2 [ m + h ] : 259.1693 ; found : 259.1690 . in a dry flask , 2-cinnamyl-2-(prop-2-yn-1-yl)propane-1,3-diol 
 ( 200 mg , 0.87 mmol ) was dissolved in anhydrous thf ( 2 ml ) , and nah 
 ( 73 mg , 1.82 mmol ) , pmb - cl ( 0.26 ml , 1.91 mmol ) , and tbai ( 48 mg , 
 0.13 mmol ) were added sequentially .
the suspension was stirred vigorously 
 at rt for 24 h. tlc showed full consumption of starting material and 
 conversion to mono- and diprotected alcohols ( diprotection major ) . 

the mixture was quenched by careful addition of saturated aqueous 
 nh4cl ( 30 ml ) and extracted with diethyl ether ( 3  
 50 ml ) .
the combined organic layers were washed with brine ( 2  
 15 ml ) , dried over mgso4 , and filtered , and the solvent 
 was removed under vacuum .
the resulting mixture was purified by column 
 chromatography on silica gel eluting with c - hexane / etoac 10:1 to afford 
 230 mg of a colorless oil ( 64% ) . h 
 nmr ( 500 mhz , cdcl3 )  7.347.23 ( m , 
 8h ) , 7.237.18 ( m , 1h ) , 6.896.84 ( m , 4h ) , 6.39 ( d , j = 15.7 hz , 1h ) , 6.12 ( dt , j = 15.6 , 7.7 
 hz , 1h ) , 4.45 ( s , 4h ) , 3.81 ( s , 6h ) , 3.423.36 ( m , 4h ) , 2.35 
 ( dd , j = 7.7 , 1.3 hz , 2h ) , 2.31 ( d , j = 2.7 hz , 2h ) , 1.98 ( t , j = 2.7 hz , 1h ) ppm .
c nmr ( 126 mhz , cdcl3 )  159.0 , 137.7 , 132.9 , 130.8 , 129.1 , 128.4 , 126.9 , 126.1 , 
 125.9 , 113.7 , 81.4 , 72.9 , 71.4 , 70.2 , 55.2 , 42.6 , 35.4 , 22.4 ppm .
hrms - esi calcd for c31h34o4na [ m + na ] : 493.2349 ; found : 493.2362 .
enyne ( 1 equiv ) and aniline ( 1.1 equiv ) were 
 placed in a dry flask , and [ johnphosau(mecn)]sbf6 ( a ) ( 2 mol % ) was added as a solution in anhydrous ch2cl2 ( overall 0.15 m ) .
the solution was stirred vigorously 
 at rt for 16 h. obtained using catalyst a ( 2.2 
 mg , 2.8 mol ) , enyne 1a ( 0.14 ml , 1.0 m in dry 
 ch2cl2 , 0.14 mmol ) , and aniline ( 0.30 ml , 0.5 
 m in dry ch2cl2 , 0.154 mmol ) as the nucleophile 
 in ch2cl2 ( 0.6 ml ) according to general procedure 
 i. preparative tlc ( c - hexane / etoac 5:1 ) yielded 49 mg ( 93% ) of the 
 aminated product as a colorless oil .
h nmr ( 400 mhz , cdcl3 )  7.417.40 
 ( m , 2h ) , 7.397.36 ( m , 2h ) , 7.26 ( tt , j = 
 4.2 , 1.5 hz , 1h ) , 7.10 ( dd , j = 8.6 , 7.4 hz , 2h ) , 
 6.67 ( tt , j = 7.4 , 1.2 hz , 1h ) , 6.54 ( dd , j = 8.6 , 1.2 hz , 2h ) , 5.105.08 ( m , 1h ) , 4.804.78 
 ( m , 1h ) , 4.57 ( d , j = 5.0 hz , 1h ) , 4.34 ( s , 1h ) , 
 3.78 ( s , 3h ) , 3.71 ( s , 3h ) , 3.163.07 ( m , 2h ) , 3.012.96 
 ( m , 1h ) , 2.392.33 ( m , 1h ) , 2.282.24 ( m , 1h ) ppm .
c nmr ( 101 mhz , cdcl3 )  172.4 , 171.8 , 147.8 , 147.2 , 142.3 , 129.0 , 128.5 , 127.0 , 
 126.7 , 117.5 , 113.7 , 109.1 , 59.0 , 58.2 , 52.9 , 52.8 , 49.4 , 42.0 , 34.9 
 ppm . hrms - esi calcd for c23h26no4 [ m + h ] : 380.1856 ; found : 380.1865 .
obtained using catalyst a ( 5.6 
 mg , 7.4 mol ) , enyne 1a ( 42 mg , 0.15 mmol ) and p - anisidine ( 19 mg , 0.16 mol ) as the nucleophile in ch2cl2 ( 1.0 ml ) according to the general procedure 
 i. purification by column chromatography ( n - hexane / etoac 
 9:1 ) yielded 28 mg ( 47% ) of the aminated product as a yellow oil .
h nmr ( 400 mhz , cdcl3 )  7.387.18 ( m , 5h ) , 6.706.65 ( m , 2h ) , 6.476.42 
 ( m , 2h ) , 5.06 ( br s , 1h ) , 4.77 ( br s , 1h ) , 4.44 ( d , j =   4.6 hz , 1h ) , 3.98 ( s , 1h ) , 3.73 ( s , 3h ) , 3.67 ( s , 6h ) , 3.202.95 
 ( m , 3h ) , 2.32 ( dd , j =   13.6 , 9.8 hz , 1h ) , 2.23 ( dd , j =   13.6 , 8.7 hz , 1h ) ppm .
c nmr ( 101 mhz , cdcl3 )  172.4 , 172.0 , 152.2 , 
 147.6 , 142.6 , 142.2 , 128.7 , 127.1 , 126.9 , 115.1 , 114.8 , 109.1 , 60.0 , 
 57.9 , 55.8 , 53.0 , 52.9 , 49.7 , 42.1 , 35.0 ppm .
hrms - esi calcd for c24h28no5 [ m + h ] : 410.1962 ; found : 410.1984 . obtained using catalyst a ( 2.2 
 mg , 2.8 mol ) , enyne 1a ( 0.14 ml , 1.0 m in dry 
 ch2cl2 , 0.14 mmol ) , and 2-bromoaniline ( 26 mg , 
 0.15 mmol ) as the nucleophile in ch2cl2 ( 0.85 
 ml ) according to general procedure i. preparative tlc ( c - hexane / etoac 
 5:1 ) yielded 56 mg ( 87% ) of the aminated product as a colorless oil .
h nmr ( 400 mhz , cdcl3 )  7.41 ( dd , j = 7.9 , 1.4 hz , 1h ) , 7.357.31 
 ( m , 4h ) , 7.277.24 ( m , 1h ) , 6.99 ( dt , j = 
 7.6 , 1.4 hz , 1h ) , 6.53 ( dt , j = 7.6 , 1.4 hz , 1h ) , 
 6.36 ( dd , j = 7.6 , 1.4 hz , 1h ) , 5.09 ( m , 1h ) , 4.80 
 ( d , j = 4.7 hz , 1h ) , 4.72 ( m , 1h ) , 4.52 ( t , j = 5.3 hz , 1h ) , 3.74 ( s , 3h ) , 3.71 ( s , 3h ) , 3.183.16 
 ( m , 1h ) , 3.03 ( s , 2h ) , 2.45 ( dd , j = 13.7 , 8.2 hz , 
 1h ) , 2.29 ( dd , j = 13.7 , 9.9 hz , 1h ) ppm .
c nmr ( 101 mhz , cdcl3 )  
 171.8 , 171.7 , 146.9 , 144.3 , 141.2 , 132.2 , 128.5 , 128.2 , 127.3 , 126.8 , 
 118.1 , 112.9 , 110.3 , 109.9 , 60.3 , 58.1 , 52.9 , 52.8 , 49.4 , 42.1 , 35.5 
 ppm .
hrms - esi calcd for c23h25brno4 [ m + h ] : 458.0961 ; found : 458.0969 . obtained using catalyst a ( 5.7 
 mg , 7.4 mol ) , enyne 1a ( 42 mg , 0.15 mmol ) , and 
 4-bromoaniline ( 31 mg , 0.18 mol ) as the nucleophile in ch2cl2 ( 1.0 ml ) according to general procedure i. purification 
 by column chromatography ( pentane / diethyl ether 9:1 to 4:1 ) yielded 
 50 mg ( 74% ) of the aminated product as a white solid , which was further 
 crystallized from et2o / pentane .
h nmr ( 400 mhz , cdcl3 )  7.407.22 
 ( m , 5h ) , 7.187.14 ( m , 2h ) , 6.436.36 ( m , 2h ) , 5.08 
 ( br s , 1h ) , 4.78 ( br s , 1h ) , 4.554.50 ( m , 2h ) , 3.78 ( s , 3h ) , 
 3.71 ( s , 3h ) , 3.143.05 ( m , 2h ) , 2.992.92 ( m , 1h ) , 
 2.35 ( dd , j =   14.0 , 9.3 hz , 1h ) , 2.21 ( dd , j =   14.0 , 9.3 hz , 1h ) ppm .
c nmr ( 101 mhz , cdcl3 )  172.7 , 171.9 , 147.2 , 
 146.9 , 141.9 , 131.8 , 128.8 , 127.3 , 126.7 , 115.3 , 109.2 , 109.1 , 58.9 , 
 57.7 , 53.1 , 52.9 , 49.3 , 42.2 , 34.7 ppm .
hrms - esi calcd 
 for c23h25brno4 [ m + 
 h ] : 458.0961 ; found : 458.0971 .
mp 124126 
 c . obtained using catalyst a ( 15 
 mg , 20 mol ) , enyne 1a ( 286 mg , 1 mmol ) , and 2-iodoaniline 
 ( 234 mg , 1.07 mmol ) as the nucleophile in ch2cl2 ( 4 ml ) according to general procedure i. purification by column 
 chromatography ( pentane / diethyl ether 9:1 to 4:1 ) yielded 489 mg ( 98% ) 
 of the aminated product as a colorless solid . note : on 2.79 mmol scale , the reaction afforded the desired compound in 
 90% yield .
h nmr ( 500 mhz , cdcl3 )  7.64 ( dd , j = 7.8 , 1.5 hz , 1h ) , 
 7.367.30 ( m , 4h ) , 7.287.22 ( m , 1h ) , 7.00 ( ddd , j = 8.2 , 6.8 , 1.5 hz , 1h ) , 6.39 ( ddd , j = 7.8 , 7.3 , 1.5 hz , 1h ) , 6.27 ( dd , j = 8.2 , 1.5 
 hz , 1h ) , 5.10 ( q , j = 2.2 hz , 1h ) , 4.76 ( q , j = 2.2 hz , 1h ) , 4.61 ( d , j = 4.6 hz , 1h ) , 
 4.52 ( t , j = 5.1 hz , 1h ) , 3.73 ( s , 3h ) , 3.70 ( s , 
 3h ) , 3.16 ( dtt , j = 12.3 , 5.5 , 2.3 hz , 1h ) , 3.112.99 
 ( m , 2h ) , 2.42 ( ddd , j = 13.7 , 8.1 , 1.4 hz , 1h ) , 2.28 
 ( dd , j = 13.7 , 10.1 hz , 1h ) ppm .
c nmr ( 126 mhz , cdcl3 )  171.8 , 
 171.7 , 147.0 , 146.4 , 141.1 , 138.8 , 129.1 , 128.6 , 127.3 , 126.8 , 119.0 , 
 112.2 , 110.0 , 86.2 , 60.7 , 58.2 , 52.9 , 52.8 , 49.5 , 42.1 , 35.5 ppm .
hrms - esi calcd for c23h24ino4na [ m + na ] : 528.0642 , found 528.0637 .
mp 129131 c . obtained using catalyst a ( 19 
 mg , 24 mol ) , enyne 1a ( 350 mg , 1.22 mmol ) , and 
 4-bromo-2-iodoaniline ( 401 mg , 1.35 mmol ) as the nucleophile in ch2cl2 ( 8 ml ) according to general procedure i. purification 
 by column chromatography ( pentane / et2o 9:1 ) yielded 644 
 mg ( 90% ) of the aminated product as a white solid .
h nmr ( 500 mhz , cdcl3 )  7.72 
 ( d , j = 2.3 hz , 1h ) , 7.357.21 ( m , 5h ) , 7.07 
 ( dd , j = 8.7 , 2.3 hz , 1h ) , 6.11 ( d , j = 8.7 hz , 1h ) , 5.10 ( q , j = 2.2 hz , 1h ) , 4.74 ( q , j = 2.2 hz , 1h ) , 4.61 ( d , j = 4.5 hz , 1h ) , 
 4.47 ( t , j = 5.0 hz , 1h ) , 3.72 ( s , 3h ) , 3.69 ( s , 
 3h ) , 3.183.11 ( m , 1h ) , 3.03 ( bs , 2h ) , 2.39 ( dd , j = 13.7 , 8.2 hz , 1h ) , 2.24 ( dd , j = 13.7 , 10.2 hz , 
 1h ) ppm .
c nmr ( 126 mhz , cdcl3 )  171.9 , 171.8 , 147.1 , 145.8 , 140.7 , 140.3 , 132.0 , 
 128.8 , 127.7 , 126.9 , 113.3 , 110.3 , 109.4 , 86.3 , 60.9 , 58.3 , 53.1 , 
 53.0 , 49.5 , 42.3 , 35.6 ppm .
hrms - esi calcd for c23h23brino4na [ m + na ] : 605.9747 ; found : 605.9747 .
mp 123125 
 c . obtained using catalyst a ( 19 
 mg , 24 mol ) , enyne 1a ( 350 mg , 1.22 mmol ) , and 
 5-chloro-2-iodoaniline ( 341 mg , 1.35 mmol ) as the nucleophile in ch2cl2 ( 8 ml ) according to general procedure i. purification 
 by column chromatography ( pentane / et2o 9:1 ) yielded 562 
 mg ( 85% ) of the aminated product as a white solid .
h nmr ( 500 mhz , cdcl3 )  7.51 
 ( d , j = 8.3 hz , 1h ) , 7.377.29 ( m , 4h ) , 7.287.23 
 ( m , 1h ) , 6.39 ( dd , j = 8.3 , 2.3 hz , 1h ) , 6.24 ( d , j = 2.3 hz , 1h ) , 5.09 ( q , j = 2.1 hz , 1h ) , 
 4.73 ( q , j = 2.2 hz , 1h ) , 4.68 ( d , j = 5.0 hz , 1h ) , 4.49 ( t , j = 5.3 hz , 1h ) , 3.72 ( s , 
 3h ) , 3.69 ( s , 3h ) , 3.203.12 ( m , 1h ) , 3.052.99 ( m , 
 2h ) , 2.42 ( dd , j = 13.7 , 8.1 hz , 1h ) , 2.23 ( dd , j = 13.7 , 10.1 hz , 1h ) ppm .
c nmr ( 126 mhz , cdcl3 )  171.9 , 171.8 , 147.5 , 
 147.0 , 140.5 , 139.4 , 135.4 , 128.9 , 127.7 , 126.9 , 119.1 , 112.2 , 110.3 , 
 83.2 , 60.7 , 58.3 , 53.1 , 53.0 , 49.4 , 42.3 , 35.6 ppm .
hrms - esi calcd for c23h23clino4na [ m + na ] : 562.0253 ; found : 562.0262 .
mp 143145 c . obtained using catalyst a ( 2.2 
 mg , 2.8 mol ) , enyne 1a ( 0.14 ml , 1.0 m in dry 
 ch2cl2 , 0.14 mmol ) , and 2,4,6-trimethylaniline 
 ( 0.31 ml , 0.5 m in ch2cl2 , 0.15 mmol ) as the 
 nucleophile in ch2cl2 ( 0.6 ml ) according to 
 general procedure i. preparative tlc ( c - hexane / etoac 5:1 ) yielded 
 48 mg ( 82% ) of the aminated product as a colorless oil .
h nmr ( 400 mhz , cdcl3 )  
 7.217.14 ( m , 5h ) , 6.68 ( s , 2h ) , 4.86 ( d , j = 1.7 hz , 1h ) , 4.36 ( d , j = 1.7 hz , 1h ) , 4.22 ( d , j = 8.4 hz , 1h ) , 3.77 ( s , 3h ) , 3.75 ( s , 3h ) , 3.45 ( s , 1h ) , 
 3.293.25 ( m , 1h ) , 2.982.87 ( m , 3h ) , 2.42 ( dd , j = 13.8 , 9.5 hz , 1h ) , 2.16 ( s , 3h ) , 2.10 ( s , 6h ) ppm .
c nmr ( 101 mhz , cdcl3 )  172.2 , 172.0 , 148.2 , 142.8 , 141.5 , 130.2 , 129.6 , 128.4 , 
 128.0 , 127.4 , 127.0 , 110.0 , 64.0 , 58.1 , 52.9 , 52.8 , 47.9 , 42.2 , 37.8 , 
 20.4 , 19.3 ppm . hrms - esi calcd for c26h32no4 [ m + h ] : 422.2326 ; 
 found : 422.2331 .
obtained using catalyst a ( 5.7 
 mg , 7.4 mol ) , enyne 1a ( 41 mg , 0.14 mmol ) and 
 3,5-bistrifluoromethylaniline ( 25 l , 0.16 mol ) 
 as the nucleophile in ch2cl2 ( 1.0 ml ) according 
 to general procedure i. purification by column chromatography ( c - hexane / etoac 
 12:1 ) yielded 67 mg ( 89% ) of the aminated product as a white solid .
h nmr ( 400 mhz , cdcl3 )  7.367.30 ( m , 4h ) , 7.307.23 ( m , 1h ) , 7.07 
 ( br s , 1h ) , 6.856.81 ( m , 2h ) , 5.27 ( d , j = 
 4.6 hz , 1h ) , 5.105.05 ( m , 1h ) , 4.794.76 ( m , 1h ) , 4.62 
 ( dd , j = 4.6 hz , 1h ) , 3.78 ( s , 3h ) , 3.69 ( s , 3h ) , 
 3.203.13 ( m , 1h ) , 3.133.08 ( m , 1h ) ,
2.932.86 
 ( m , 1h ) , 2.39 ( dd , j =   14.2 , 8.5 hz , 1h ) , 2.18 ( dd , j =   14.6 , 10.4 hz , 1h ) ppm .
c nmr ( 101 mhz , cdcl3 )  173.2 , 171.7 , 148.6 , 
 147.0 , 140.7 , 132.2 ( q , j = 32.9 hz ) , 129.1 , 127.8 , 
 126.6 , 123.6 ( q , j = 273.4 hz ) , 112.7 , 110.3 ( sept , j = 4.1 hz ) , 109.2 , 58.4 , 57.6 , 53.4 , 53.0 , 48.8 , 42.4 , 
 34.4 ppm .
f nmr ( 376.49 mhz , 
 cdcl3 )  63.0 ppm . hrms - esi calcd 
 for c25h23f6no4na [ m + na ] : 538.1423 ; found : 538.1437 .
mp 143145 c . obtained using catalyst a ( 2.2 
 mg , 2.8 mol ) , enyne 1a ( 0.14 ml , 1.0 m in dry 
 ch2cl2 , 0.14 mmol ) , and naphtalen-1-amine ( 20 
 mg , 0.14 mmol ) as the nucleophile in ch2cl2 ( 0.8 
 ml ) according to general procedure i. preparative tlc ( c - hexane / etoac 
 5:1 ) yielded 31 mg ( 51% ) of the aminated product as a colorless oil .
h nmr ( 400 mhz , cdcl3 )  8.10 ( br d , j = 7.9 hz , 1h ) , 7.80 ( dd , j = 7.6 , 1.8 hz , 1h ) , 7.547.44 ( m , 4h ) , 7.34 ( t , j = 7.2 hz , 2h ) , 7.287.24 ( m , 1h ) , 7.217.14 
 ( m , 2h ) , 6.33 ( dd , j = 7.2 , 1.2 hz , 1h ) , 5.09 ( d , j = 2.2 hz , 1h ) , 4.85 ( d , j = 2.2 hz , 1h ) , 
 4.80 ( d , j = 4.7 hz , 1h ) , 3.82 ( s , 3h ) , 3.73 ( s , 
 3h ) , 3.323.28 ( m , 1h ) , 3.15 ( d , j = 16.2 
 hz , 1h ) , 3.02 ( dd , j = 16.2 , 1.9 hz , 1h ) , 2.58 ( dd , j = 14.0 , 9.6 hz , 1h ) , 2.30 ( dd , j = 14.0 , 
 9.6 hz , 1h ) ppm .
c nmr ( 101 
 mhz , cdcl3 )  172.5 , 171.8 , 147.2 , 142.6 , 141.9 , 
 134.2 , 128.6 , 127.1 , 126.6 , 126.4 , 125.6 , 124.7 , 123.9 , 120.2 , 117.5 , 
 109.1 , 106.4 , 58.7 , 57.6 , 52.9 , 52.7 , 49.4 , 42.3 , 34.7 ppm .
hrms - esi calcd for c27h28no4 [ m + h ] : 430.2013 ; found : 430.2020 . obtained using catalyst a ( 2.2 
 mg , 2.8 mol ) , enyne 1a ( 0.14 ml , 1.0 m in dry 
 ch2cl2 , 0.14 mmol ) , and quinolin-8-amine ( 20 
 mg , 0.14 mmol ) as the nucleophile in ch2cl2 ( 0.8 
 ml ) according to general procedure i. preparative tlc ( c - hexane / etoac 
 5:1 ) yielded 28 mg ( 46% ) of the aminated product as a colorless oil . h nmr ( 400 mhz , cdcl3 )  8.79 ( dd , j = 4.0 , 1.6 hz , 1h ) , 8.05 ( dd , j = 8.0 , 1.6 hz , 1h ) , 7.43 ( d , j = 8.4 
 hz , 2h ) , 7.38 ( dd , j = 8.0 , 4.0 hz , 1h ) , 7.32 ( t , j = 7.2 hz , 2h ) , 7.247.19 ( m , 2h ) , 7.01 ( dd , j = 8.4 , 0.8 hz , 1h ) , 6.78 ( d , j = 6.0 
 hz , 1h ) , 6.45 ( dd , j = 7.6 , 0.8 hz , 1h ) , 5.01 ( d , j = 2.0 hz , 1h ) , 4.62 ( t , j = 6.4 hz , 1h ) , 
 4.58 ( d , j = 2.0 hz , 1h ) , 3.74 ( s , 3h ) , 3.73 ( s , 
 3h ) , 3.293.25 ( m , 1h ) , 3.13 ( qd , j = 16.4 , 
 2.4 hz , 1h ) , 3.01 ( qd , j = 16.4 , 2.4 hz , 1h ) , 2.63 
 ( ddd .
j = 14.0 , 9.6 , 1.6 , hz , 1h ) , 2.39 ( dd , j = 14.0 , 9.6 hz , 1h ) ppm .
c nmr ( 101 mhz , cdcl3 )  171.9 , 171.8 , 147.1 , 
 147.0 , 143.9 , 142.0 , 138.4 , 135.9 , 128.5 , 128.4 , 127.5 , 127.2 , 127.1 , 
 121.3 , 114.2 , 109.9 , 106.2 , 60.3 , 58.4 , 52.8 , 49.4 , 41.9 , 36.2 ppm .
hrms - esi calcd for c26h27n2o4 [ m + h ] : 431.1965 ; found : 431.1954 . obtained using catalyst a ( 2.2 
 mg , 2.8 mol ) , enyne 1a ( 0.14 ml , 1.0 m in dry 
 ch2cl2 , 0.14 mmol ) , and n - methylaniline 
 ( 0.3 ml , 0.5 m in dry ch2cl2 , 0.15 mmol ) as 
 the nucleophile in ch2cl2 ( 0.6 ml ) according 
 to general procedure i. preparative tlc ( c - hexane / etoac 5:1 ) yielded 
 50 mg ( 92% ) of the aminated product as a colorless oil .
h nmr ( 400 mhz , cdcl3 )  
 7.277.23 ( m , 7h ) , 6.896.86 ( m , 2h ) , 6.75 ( tt , j = 7.2 , 1.0 hz , 1h ) , 4.864.81 ( m , 2h ) , 4.22 ( d , j = 2.1 hz , 1h ) , 3.79 ( s , 3h ) , 3.70 ( s , 3h ) , 3.603.57 
 ( m , 1h ) , 3.24 ( qd , j = 16.5 , 2.1 hz , 1h ) , 3.01 ( dd , j = 16.6 , 2.1 hz , 1h ) , 2.74 ( ddd , j = 13.5 , 
 7.7 , 1.5 hz , 1h ) , 2.67 ( s , 3h ) , 2.12 ( dd , j = 13.5 , 
 9.9 hz , 1h ) ppm .
c nmr ( 101 
 mhz , cdcl3 )  172.4 , 171.9 , 150.1 , 148.6 , 138.9 , 
 129.2 , 128.1 , 128.0 , 127.3 , 117.3 , 113.9 , 109.8 , 65.7 , 57.6 , 52.9 , 
 52.8 , 43.4 , 41.8 , 38.6 , 31.8 ppm .
hrms - esi calcd for 
 c24h28no4 [ m + h ] : 394.2013 ; found : 394.2026 . obtained using catalyst a ( 1.9 
 mg , 2.5 mol ) , enyne 1b ( 0.12 ml ,
1.0 m in dry 
 ch2cl2 , 0.12 mmol ) , and aniline ( 0.25 ml , 0.5 
 m in ch2cl2 , 0.124 mmol ) as the nucleophile 
 in ch2cl2 ( 0.6 ml ) according to general procedure 
 i. preparative tlc ( c - hexane / etoac 5:1 ) yielded 58 mg ( 94% ) of the 
 aminated product as a colorless oil .
h nmr ( 400 mhz , cdcl3 )  8.09 ( dd , j = 6.4 , 0.8 hz , 2h ) , 7.97 ( dd , j = 5.6 , 
 0.8 hz , 2h ) , 7.757.69 ( m , 2h ) , 7.62 ( t , j = 6.0 hz , 2h ) , 7.54 ( t , j = 6.4 hz , 2h ) , 7.19 ( dd , j = 6.8 , 6.0 hz , 2h ) , 6.81 ( t , j = 6.0 
 hz , 2h ) , 6.68 ( dd , j = 7.2 , 6.8 hz , 1h ) , 5.02 ( br 
 s , 2h ) , 3.63 ( br s , 1h ) , 3.55 ( qd , j = 14.0 , 2.0 
 hz , 1h ) , 3.35 ( dt , j = 14.0 , 2.0 hz , 1h ) , 2.912.82 
 ( m , 2h ) , 2.67 ( ddd , j = 12.4 , 7.2 , 1.2 , hz , 1h ) , 
 1.39 ( s , 3h ) , 1.30 ( s , 3h ) ppm .
c 
 nmr ( 101 mhz , cdcl3 )  146.6 , 145.8 , 137.2 , 
 135.8 , 134.7 , 134.5 , 131.0 , 130.9 , 129.2 , 128.7 , 128.6 , 118.5 , 116.8 , 
 111.3 , 91.7 , 56.4 , 50.2 , 41.0 , 33.6 , 26.2 , 25.4 ppm .
hrms - esi calcd for c27h30no4s2 [ m + h ] : 496.1611 ; found : 496.1638 . obtained using catalyst a ( 1.9 
 mg , 2.5 mol ) , enyne 1b ( 0.12 ml , 1.0 m in dry 
 ch2cl2 , 0.12 mmol ) , and 4-methoxyaniline ( 15 
 mg , 0.12 mmol ) as the nucleophile in ch2cl2 ( 0.8 
 ml ) according to general procedure i. preparative tlc ( c - hexane / etoac 
 5:1 ) yielded 59 mg ( 90% ) of the aminated product as a colorless oil .
h nmr ( 400 mhz , cdcl3 )  8.10 ( dd , j = 8.0 , 0.8 hz , 2h ) , 7.99 ( dd , j = 8.4 , 1.2 hz , 2h ) , 7.757.71 ( m , 2h ) , 7.62 ( t , j = 8.0 hz , 2h ) , 7.55 ( t , j = 8.0 hz , 2h ) , 
 6.78 ( d , j = 9.2 hz , 2h ) , 6.72 ( d , j = 9.2 hz , 2h ) , 5.08 ( s , 1h ) , 5.04 ( s , 1h ) , 3.80 ( s , 3h ) , 3.56 ( qd , j = 17.2 , 2.4 hz , 1h ) , 3.16 ( dt , j = 8.4 , 
 2.0 hz , 1h ) , 2.922.83 ( m , 2h ) , 2.69 ( ddd , j = 16.8 , 8.8 , 1.2 , hz , 1h ) , 1.27 ( s , 3h ) , 1.20 ( s , 3h ) ppm .
c nmr ( 101 mhz , cdcl3 )  153.9 , 146.8 , 139.1 , 137.2 , 135.9 , 134.6 , 134.5 , 131.0 , 
 131.0 , 128.7 , 128.6 , 121.4 , 114.4 , 111.4 , 91.8 , 57.0 , 55.6 , 51.3 , 
 40.9 , 33.8 , 26.2 , 25.3 ppm . hrms - esi calcd for c28h32no5s2 [ m 
 + h ] : 526.1716 ; found : 526.1726 .
obtained using catalyst a ( 1.9 
 mg , 2.5 mol ) , enyne 1b ( 0.12 ml , 1.0 m in dry 
 ch2cl2 , 0.12 mmol ) , and 2-bromoaniline ( 21 mg , 
 0.124 mmol ) as the nucleophile in ch2cl2 ( 0.8 
 ml ) according to general procedure i. preparative tlc ( c - hexane / etoac 
 5:1 ) yielded 53 mg ( 74% ) of the aminated product as a colorless solid .
h nmr ( 400 mhz , cdcl3 )  8.11 ( dd , j = 8.8 , 1.2 hz , 2h ) , 8.01 ( dd , j = 8.8 , 1.2 hz , 2h ) , 7.747.70 ( m , 2h ) , 7.637.54 
 ( m , 4h ) , 7.46 ( dd , j = 7.6 , 1.2 hz , 1h ) , 7.15 ( dt , j = 8.4 , 2.0 hz , 1h ) , 6.90 ( dd , j = 8.4 , 
 2.4 hz , 1h ) , 6.61 ( dt , j = 8.0 , 1.2 hz , 1h ) , 5.06 
 ( s , 1h ) , 5.00 ( s , 1h ) , 4.43 ( br s , 1h ) , 3.61 ( qd , j = 17.2 , 2.4 hz , 1h ) , 3.47 ( t , j = 7.6 hz , 1h ) , 
 2.84 ( d , j = 17.6 hz , 1h ) , 2.73 ( dd , j = 15.6 , 8.4 hz , 1h ) , 2.58 ( ddd , j = 15.6 , 9.2 , 
 1.6 hz , 1h ) , 1.49 ( s , 3h ) , 1.34 ( s , 3h ) ppm . c nmr ( 101 mhz , cdcl3 )  146.4 , 142.7 , 
 137.0 , 135.7 , 134.7 , 134.6 , 132.9 , 131.1 , 131.0 , 128.7 , 128.7 , 128.2 , 
 118.5 , 114.5 , 111.9 , 111.5 , 91.7 , 56.7 , 49.4 , 40.7 , 33.7 , 26.2 , 25.2 
 ppm .
hrms - esi calcd for c27h28brno4s2na [ m + na ] : 596.0535 ; 
 found : 596.0566 .
mp 191192 c . obtained using catalyst a ( 1.9 
 mg , 2.5 mol ) , enyne 1b ( 0.12 ml , 1.0 m in dry 
 ch2cl2 , 0.124 mmol ) , and 4-bromoaniline ( 21.4 
 mg , 0.12 mmol ) as the nucleophile in ch2cl2 ( 0.8 
 ml ) according to general procedure i. preparative tlc ( c - hexane / etoac 
 5:1 ) yielded 67 mg ( 93% ) of the aminated product as a colorless foam .
h nmr ( 400 mhz , cdcl3 )  8.07 ( dd , j = 8.4 , 1.2 hz , 2h ) , 7.05 ( dd , j = 8.4 , 1.2 hz , 2h ) , 7.767.70 ( m , 2h ) , 7.647.53 
 ( m , 4h ) , 7.277.25 ( m , 2h ) , 6.586.55 ( m , 2h ) , 5.03 
 ( s , 1h ) , 5.00 ( s , 1h ) , 3.70 ( br s , 1h ) , 3.53 ( qd , j = 17.2 , 2.4 hz , 1h ) , 3.32 ( dt , j = 8.4 , 2.4 hz , 
 1h ) , 2.87 ( d , j = 17.2 hz , 1h ) , 2.79 ( dd , j = 15.6 , 8.8 , hz 1h ) , 2.62 ( ddd , j = 15.6 , 
 8.8 , 1.6 hz , 1h ) , 1.48 ( s , 3h ) , 1.33 ( s , 3h ) ppm . c nmr ( 101 mhz , cdcl3 )  146.5 , 
 144.9 , 137.1 , 135.7 , 134.7 , 134.6 , 132.0 , 131.9 , 131.0 , 128.7 , 128.6 , 
 118.1 , 116.7 , 111.3 , 91.6 , 56.5 , 49.9 , 41.0 , 33.5 , 26.1 , 25.3 ppm . hrms - esi calcd for c27h27brno4s2 [ m  h ] : 572.0570 ; found : 572.0593 .
mp 116118 c . obtained using catalyst a ( 1.9 
 mg , 2.5 mol ) , enyne 1b ( 0.12 ml , 1.0 m in dry 
 ch2cl2 , 0.12 mmol ) and 3,5-bis(trifluoromethyl)aniline 
 ( 0.25 ml , 0.5 m in ch2cl2 , 0.12 mmol ) as the 
 nucleophile in ch2cl2 ( 0.6 ml ) according to 
 general procedure i. preparative tlc ( c - hexane / etoac 5:1 ) yielded 
 38 mg ( 48% ) of the aminated product as a colorless oil .
h nmr ( 400 mhz , cdcl3 )  
 8.09 ( dd , j = 8.4 , 1.2 hz , 2h ) , 7.98 ( dd , j = 8.4 , 1.2 hz , 2h ) , 7.777.69 ( m , 2h ) , 7.647.61 
 ( m , 2h ) , 7.567.52 ( m , 2h ) , 7.21 ( br s , 1h ) , 7.00 ( br s , 2h ) , 
 5.02 ( s , 1h ) , 4.93 ( s , 1h ) , 4.20 ( s , 1h ) , 3.54 ( qd , j = 17.6 , 2.4 , hz , 1h ) , 3.24 ( t , j = 9.2 hz , 1h ) , 
 2.97 ( d , j = 17.6 hz , 1h ) , 2.83 ( dd , j = 16.0 , 8.4 hz , 1h ) , 2.67 ( ddd , j = 16.0 , 8.4 , 
 1.6 hz , 1h ) , 1.45 ( s , 3h ) , 1.38 ( s , 3h ) ppm . c nmr ( 101 mhz , cdcl3 )  146.6 , 146.1 , 
 137.0 , 135.8 , 134.9 , 134.7 , 132.4 ( q , j = 32.0 hz ) , 
 131.0 , 130.9 , 128.8 , 128.7 , 123.4 ( q , j = 271.0 hz ) , 
 114.4 ( q , j = 4.0 hz ) , 111.8 , 110.8 ( sept , j = 4.0 hz ) , 92.3 , 56.7 , 50.2 , 41.0 , 33.3 , 25.9 , 25.2 ppm .
hrms - esi calcd for c29h26f6no4s2 [ m  h ] : 630.1213 ; found : 630.1215 . obtained using catalyst a ( 1.9 
 mg , 2.5 mol ) , enyne 1b ( 0.12 ml , 1.0 m in dry 
 ch2cl2 , 0.12 mmol ) , and naphtalen-1-amine ( 18 
 mg , 0.12 mmol ) as the nucleophile in ch2cl2 ( 0.8 
 ml ) according to general procedure i. preparative tlc ( c - hexane / etoac 
 5:1 ) yielded 50 mg ( 74% ) of the aminated product as a colorless solid .
h nmr ( 400 mhz , cdcl3 )  8.07 ( dd , j = 8.4 , 1.2 hz , 2h ) , 7.98 ( dd , j = 8.4 , 1.2 hz , 2h ) , 7.847.80 ( m , 2h ) , 7.717.66 
 ( m , 2h ) , 7.567.47 ( m , 6h ) , 7.367.31 ( m , 2h ) , 6.87 
 ( dd , j = 7.2 , 1.6 hz , 1h ) , 5.04 ( br s , 1h ) , 4.98 
 ( br s , 1h ) , 4.39 ( br s , 1h ) , 3.653.60 ( m , 2h ) , 2.912.85 
 ( m , 2h ) , 2.64 ( ddd , j = 15.6 , 8.8 , 1.6 hz , 1h ) , 1.53 
 ( s , 3h ) , 1.45 ( s , 3h ) ppm .
c nmr ( 101 mhz , cdcl3 )  146.7 , 140.9 , 137.2 , 135.8 , 
 134.7 , 134.6 , 134.5 , 131.0 , 130.9 , 128.7 , 128.6 , 125.6 , 125.0 , 124.9 , 
 119.9 , 118.3 , 111.4 , 109.1 , 91.7 , 56.5 , 49.7 , 40.9 , 33.7 , 26.1 , 25.4 
 ppm .
hrms - esi calcd for c31h31no4s2na [ m + na ] : 568.1587 ; 
 found : 568.1591 .
mp 8992 c . obtained using catalyst a ( 1.9 
 mg , 2.5 mol ) , enyne 1b ( 0.12 ml , 1.0 m in dry 
 ch2cl2 , 0.12 mmol ) , and quinolin-8-amine ( 20 
 mg , 0.12 mmol ) as the nucleophile in ch2cl2 ( 0.8 
 ml ) according to general procedure i. preparative tlc ( c - hexane / etoac 
 5:1 ) yielded slightly contaminated product .
recrystallization from 
 c - hexane / etoac yielded 49 mg ( 72% ) of the pure aminated product as 
 a pale yellow solid .
h nmr ( 400 
 mhz , cdcl3 )  8.77 ( dd , j = 4.0 , 
 1.6 hz , 1h ) , 8.07 ( dd , j = 8.4 , 2.0 hz , 1h ) , 8.04 
 ( dd , j = 8.8 , 1.2 hz , 2h ) , 7.98 ( dd , j = 8.8 , 1.2 hz , 2h ) , 7.717.41 ( m , 6h ) , 7.38 ( dd , j = 8.4 , 4.4 hz , 1h ) , 7.34 ( t , j = 8.4 
 hz , 1h ) , 7.08 ( dd , j = 8.0 , 0.8 hz , 1h ) , 6.89 ( dd , j = 8.4 , 0.8 hz , 1h ) , 6.66 ( s , 1h ) , 5.04 ( s , 1h ) , 4.97 ( s , 
 1h ) , 3.693.59 ( m , 2h ) , 2.862.77 ( m , 2h ) , 2.53 ( ddd , j = 15.6 , 8.8 , 1.6 hz ) , 1.57 ( s , 3h ) , 1.45 ( s , 3h ) ppm .
c nmr ( 101 mhz , cdcl3 )  146.8 , 146.7 , 142.0 , 138.6 , 137.0 , 136.2 , 135.6 , 134.7 , 
 134.5 , 131.0 , 130.9 , 130.8 , 129.6 , 129.1 , 128.9 , 128.7 , 128.6 , 128.5 , 
 127.5 , 121.4 , 114.3 , 111.2 , 107.2 , 91.6 , 55.9 , 48.4 , 40.8 , 33.6 , 25.8 , 
 25.0 ppm .
hrms - esi calcd for c30h31n2o4s2 [ m + h ] : 547.1720 ; found : 547.1720 .
mp 8285 c . obtained using catalyst a ( 1.9 
 mg , 2.5 mol ) , enyne 1b ( 0.12 ml , 1.0 m in dry 
 ch2cl2 , 0.12 mmol ) , and n - methylaniline 
 ( 0.25 ml , 0.5 m in ch2cl2 , 0.12 mmol ) as the 
 nucleophile in ch2cl2 ( 0.6 ml ) according to 
 general procedure i. preparative tlc ( c - hexane / etoac 5:1 ) yielded 
 53 mg ( 83% ) of the aminated product as a colorless solid .
h nmr ( 400 mhz , cdcl3 )  
 8.15 ( dd , j = 7.6 , 1.2 hz , 2h ) , 8.07 ( dd , j = 7.6 , 1.2 hz , 2h ) , 7.777.71 ( m , 2h ) , 7.667.58 
 ( m , 4h ) , 7.337.30 ( m , 2h ) , 7.177.14 ( m , 3h ) , 5.12 
 ( s , 1h ) , 5.05 ( s , 1h ) , 3.56 ( qd , j = 17.2 , 2.0 hz , 
 1h ) , 3.22 ( t , j = 7.6 hz , 1h ) , 3.08 ( dd , j = 15.6 , 8.0 hz , 1h ) , 2.80 ( d , j = 17.2 
 hz , 1h ) , 2.722.69 ( m , 1h+3h ) , 1.18 ( s , 3h ) , 0.85 ( s , 3h ) ppm .
c nmr ( 101 mhz , cdcl3 )  150.5 , 147.3 , 137.3 , 135.9 , 134.6 , 134.5 , 131.1 , 131.0 , 
 128.7 , 128.6 , 128.2 , 128.1 , 124.4 , 111.3 , 91.9 , 60.4 , 50.4 , 40.9 , 
 36.4 , 34.0 , 21.8 , 20.7 ppm .
hrms - esi calcd for c28h31no4s2na [ m 
 + na ] : 532.1587 ; found : 532.1586 .
mp 171172 
 c . obtained using catalyst a ( 2.2 
 mg , 2.8 mol ) , enyne 1c ( 35 mg , 0.15 mmol ) , and 
 aniline ( 15 l , 0.16 mol ) as the nucleophile in ch2cl2 ( 1.0 ml ) according to general procedure i. purification 
 by column chromatography ( c - hexane / etoac 13:1 ) yielded 40 mg ( 83% ) 
 of the aminated product as a colorless oil .
h nmr ( 400 mhz , cdcl3 )  7.177.11 
 ( m , 2h ) , 6.766.69 ( m , 3h ) , 5.07 ( br s , 1h ) , 4.97 ( br s , 1h ) , 
 3.72 ( s , 3h ) , 3.70 ( s , 3h ) , 3.61 ( br s , 1h ) , 3.233.19 ( m , 
 1h ) , 2.942.84 ( m , 2h ) , 2.63 ( ddd , j =   13.5 , 
 8.4 , 1.2 hz , 1h ) , 2.05 ( dd , j =   13.5 , 9.4 hz , 1h ) , 
 1.31 ( s , 3h ) , 1.29 ( s , 3h ) ppm .
c 
 nmr ( 101 mhz , cdcl3 )  172.0 , 171.9 , 148.5 , 
 146.3 , 129.2 , 118.3 , 117.2 , 111.1 , 58.6 , 56.3 , 52.8 , 49.1 , 44.0 , 36.4 , 
 27.0 , 25.9 , 25.8 ppm .
hrms - esi calcd for c19h26no4 [ m + h ] : 332.1856 ; 
 found : 332.1857 .
obtained using catalyst a ( 2.3 
 mg , 3.0 mol ) , enyne 1c ( 36 mg , 0.15 mmol ) , and p - anisidine ( 20 mg , 0.16 mmol ) as the nucleophile in ch2cl2 ( 1 ml ) according to general procedure i. purification 
 by column chromatography ( c - hexane / etoac 8:1 ) yielded 44 mg ( 81% ) 
 of the aminated product as a yellow oil .
h nmr ( 400 mhz , cdcl3 )  6.75 ( br s , 
 4h ) , 5.10 ( br s , 1h ) , 5.04 ( br s , 1h ) , 3.75 ( s , 3h ) , 3.73 ( s , 3h ) , 
 3.71 ( s , 3h ) , 3.16 ( br s , 1h ) , 3.032.83 ( m , 3h ) , 2.64 ( ddd , j =   13.4 , 8.5 , 1.7 hz , 1h ) , 2.12 ( dd , j =   13.4 , 9.3 hz , 1h ) , 1.21 ( s , 3h ) , 1.19 ( s , 3h ) ppm .
c nmr ( 101 mhz , cdcl3 )  172.1 , 
 172.0 , 154.0 , 148.7 , 139.4 , 122.0 , 114.4 , 111.3 , 58.7 , 56.9 , 55.6 , 
 52.8 , 50.4 , 44.0 , 36.4 , 27.0 , 25.9 , 25.7 ppm .
hrms - esi calcd for c20h27no5na [ m + na ] : 384.1781 ; found : 384.1801 . obtained using catalyst a ( 34 
 mg , 0.04 mmol ) , enyne 1c ( 525 mg , 2.20 mmol ) , and 2-bromoaniline 
 ( 417 mg , 2.42 mmol ) as the nucleophile in ch2cl2 ( 14 ml ) according to general procedure i. purification by column 
 chromatography ( pentane / et2o 9:1 ) yielded 649 mg ( 72% ) 
 of the aminated product as a colorless oil .
h nmr ( 500 mhz , cdcl3 )  7.43 ( dd , j = 7.9 , 1.5 hz , 1h ) , 7.12 ( ddd , j = 8.6 , 
 7.4 , 1.6 hz , 1h ) , 6.95 ( dd , j = 8.3 , 1.5 hz , 1h ) , 
 6.55 ( ddd , j = 7.9 , 7.3 , 1.5 hz , 1h ) , 5.08 ( t , j = 2.3 hz , 1h ) , 4.91 ( ddt , j = 2.9 , 1.8 , 
 0.9 hz , 1h ) , 4.43 ( s , 1h ) , 3.73 ( s , 3h ) , 3.71 ( s , 3h ) , 3.27 ( ddd , j = 9.4 , 8.5 , 2.0 hz , 1h ) , 2.95 ( dq , j = 
 15.3 , 2.6 hz , 1h ) , 2.88 ( ddt , j = 15.2 , 1.9 , 1.1 
 hz , 1h ) , 2.62 ( ddd , j = 13.6 , 8.6 , 1.9 hz , 1h ) , 2.02 
 ( dd , j = 13.6 , 9.5 hz , 1h ) , 1.38 ( s , 3h ) , 1.36 ( s , 
 3h ) ppm .
c nmr ( 126 mhz , cdcl3 )  172.0 , 171.9 , 147.9 , 143.3 , 133.0 , 128.2 , 118.1 , 
 114.8 , 112.1 , 111.5 , 58.7 , 56.7 , 52.9 , 48.8 , 44.1 , 36.4 , 25.7 , 25.6 
 ppm .
hrms - esi calcd for c19h24brno4na [ m + na ] : 432.0781 ; found : 432.0785 . obtained using catalyst a ( 2.3 
 mg , 3.0 mol ) , enyne 1c ( 35 mg , 0.15 mmol ) , and 
 4-bromoaniline ( 28 mg , 0.16 mmol ) as the nucleophile in ch2cl2 ( 1.0 ml ) according to general procedure i. purification 
 by column chromatography ( c - hexane / etoac 9:1 ) yielded 37 mg ( 62% ) 
 of the aminated product as a colorless solid .
h nmr ( 400 mhz , cdcl3 )  7.277.24 
 ( m , 2h ) , 6.656.58 ( m , 2h ) , 5.09 ( br s , 1h ) , 4.95 ( br s , 1h ) , 
 3.75 ( s , 3h ) , 3.73 ( s , 3h ) , 3.69 ( br s , 1h ) , 3.233.17 ( m , 
 1h ) , 2.90 ( br s , 2h ) , 2.62 ( dd , j =   13.5 , 8.4 hz , 
 1h ) , 2.03 ( dd , j =   13.5 , 9.3 hz , 1h ) , 1.32 ( s , 3h ) , 
 1.29 ( s , 3h ) ppm .
c nmr ( 101 
 mhz , cdcl3 )  172.0 , 171.8 , 148.3 , 145.4 , 132.0 , 
 118.4 , 111.2 , 110.1 , 58.6 , 56.4 , 52.9 , 48.9 , 44.0 , 36.4 , 25.8 ppm .
hrms - esi calcd for c19h25brno4 [ m + h ] : 410.0961 ; found : 410.0947 .
mp 116118 c . obtained using catalyst a ( 34.2 
 mg , 0.04 mmol ) , enyne 1c ( 500 mg , 2.1 mmol ) , and 2-iodoaniline 
 ( 492 mg , 2.25 mmol ) as the nucleophile in ch2cl2 ( 6.0 ml ) according to general procedure i. purification by column 
 chromatography ( pentane / et2o 10:1 to 4:1 ) yielded 553 mg 
 ( 58% ) of the aminated product as a colorless oil .
h nmr ( 500 mhz , cdcl3 )  7.68 
 ( dd , j = 7.9 , 1.6 hz , 1h ) , 7.16 ( ddd , j = 8.5 , 7.2 , 1.6 hz , 1h ) , 6.91 ( dd , j = 8.4 , 1.5 
 hz , 1h ) , 6.42 ( ddd , j = 8.0 , 7.3 , 1.4 hz , 1h ) , 5.10 
 ( br s , 1h ) , 4.92 ( br s , 1h ) , 4.25 ( s , 1h ) , 3.74 ( s , 3h ) , 3.72 ( s , 
 3h ) , 3.313.25 ( m , 1h ) , 2.97 ( dq , j = 15.2 , 
 2.6 hz , 1h ) , 2.90 ( d , j = 15.3 hz , 1h ) , 2.63 ( ddd , j = 13.7 , 8.6 , 2.0 hz , 1h ) , 2.04 ( dd , j = 13.6 , 9.5 hz , 1h ) , 1.40 ( s , 3h ) , 1.36 ( s , 3h ) ppm .
c nmr ( 126 mhz , cdcl3 )  
 171.7 , 171.7 , 147.7 , 145.4 , 139.6 , 129.0 , 118.8 , 113.8 , 111.4 , 88.7 , 
 58.5 , 56.9 , 52.7 , 48.6 , 43.9 , 36.2 , 25.6 , 25.3 ppm .
hrms - esi calcd for c19h24ino4na [ m + na ] : 480.0642 , found 480.0638 .
obtained using catalyst a ( 2.3 
 mg , 2.9 mol ) , enyne 1c ( 0.15 ml , 1.0 m in dry 
 ch2cl2 , 0.15 mmol ) , and 1-(4-aminophenyl)ethanone 
 ( 20 mg , 0.15 mmol ) as the nucleophile in ch2cl2 ( 0.8 ml ) according to general procedure i. preparative tlc
( c - hexane / etoac 
 5:1 ) yielded 40 mg ( 74% ) of the aminated product as a colorless oil .
h nmr ( 400 mhz , cdcl3 )  7.877.85 ( m , 2h ) , 6.696.66 ( m , 2h ) , 5.09 
 ( s , 1h ) , 4.91 ( s , 1h ) , 4.31 ( s , 1h ) , 3.75 ( s , 3h ) , 3.73 ( s , 3h ) , 3.37 
 ( t , j = 9.2 hz , 1h ) , 2.92 ( s , 2h ) , 2.65 ( dd , j = 13.6 , 8.8 hz , 1h ) , 2.51 ( s , 3h ) , 2.00 ( dd , j = 13.6 , 8.8 hz , 1h ) , 1.41 ( s , 3h ) , 1.39 ( s , 3h ) ppm .
c nmr ( 101 mhz , cdcl3 )  
 196.2 , 171.8 , 171.6 , 150.5 , 147.9 , 130.7 , 126.6 , 113.7 , 111.0 , 58.4 , 
 56.3 , 52.8 , 48.0 , 43.9 , 36.2 , 26.0 , 25.5 , 25.4 ppm .
hrms - esi calcd for c21h26no5 [ m  h ] : 372.1816 ; found : 372.1817 . obtained using catalyst a ( 2.4 mg , 3 mol ) , enyne 1c ( 35 mg , 0.14 mmol ) , 
 and 3,5-bis(trifluoromethyl)aniline ( 25 l , 0.16 
 mmol ) as the nucleophile in ch2cl2 ( 1.0 ml ) 
 according to general procedure i. preparative tlc ( c - hexane / etoac 
 15:1 ) yielded 28 mg ( 42% ) of the aminated product as a colorless oil .
h nmr ( 400 mhz , cdcl3 )  7.16 ( s , 1h ) , 7.04 ( s , 2h ) , 5.155.12 ( m , 1h ) , 4.994.96 
 ( m , 1h ) , 4.17 ( br s , 1h ) , 3.74 ( s , 3h ) , 3.72 ( s , 3h ) , 3.18 ( dddd , j = 10.3 , 8.6 , 4.0 , 2.0 hz , 1h ) , 2.94 ( dq , j = 15.3 , 1.2 hz , 1h ) , 2.88 ( dq , j = 15.4 , 2.6 hz , 
 1h ) , 2.62 ( ddd , j = 13.6 , 8.5 , 1.8 hz , 1h ) , 2.04 
 ( dd , j = 13.6 , 9.6 hz , 1h ) , 1.40 ( s , 3h ) , 1.36 ( s , 
 3h ) ppm .
c nmr ( 101 mhz , cdcl3 )  171.7 , 171.5 , 147.8 , 147.0 , 132.3 ( q , j = 32.7 hz ) , 123.5 ( q , j = 272.7 hz ) , 114.6 ( app . 

d , j = 4.2 hz ) , 111.4 , 110.5 ( quintet , j = 3.7 hz ) , 58.3 , 56.5 , 52.8 , 52.8 , 49.0 , 43.8 , 36.1 , 25.6 , 25.3 
 ppm .
hrms - esi calcd for 
 c21h23f6no4na [ m + na ] : 490.1423 ; found : 490.1430 . obtained using catalyst a ( 2.3 mg , 2.9 mol ) , enyne 1c ( 0.15 ml , 1.0 m 
 in dry ch2cl2 , 0.15 mmol ) , and naphtalen-1-amine 
 ( 21 mg , 0.15 mmol ) as the nucleophile in ch2cl2 ( 0.8 ml ) according to general procedure i. preparative tlc
( c - hexane / etoac 
 5:1 ) yielded 44 mg ( 78% ) of the aminated product as a colorless oil .
h nmr ( 400 mhz , cdcl3 )  7.827.78 ( m , 2h ) , 7.487.43 ( m , 2h ) , 7.34 
 ( t , j = 8.0 hz , 1h ) , 7.26 ( d , j = 
 8.0 hz , 1h ) , 6.97 ( d , j = 7.6 hz , 1h ) , 5.10 ( br s , 
 1h ) , 4.94 ( br s , 1h ) , 4.41 ( s , 1h ) , 3.75 ( s , 3h ) , 3.74 ( s , 3h ) , 3.48 
 ( dt , j = 9.2 , 1.6 hz , 1h ) , 3.032.92 ( m , 2h ) , 
 2.72 ( ddd , j = 13.6 , 8.8 , 1.6 hz , 1h ) , 2.14 ( dd , j = 13.6 , 8.8 hz , 1h ) , 1.47 ( s , 3h ) , 1.46 ( s , 3h ) ppm . c nmr ( 101 mhz , cdcl3 )  171.9 , 171.8 , 148.3 , 140.9 , 134.7 , 128.9 , 126.2 , 125.5 , 
 125.1 , 124.8 , 120.1 , 117.9 , 111.2 , 109.3 , 58.6 , 55.5 , 52.8 , 48.7 , 
 44.0 , 36.4 , 25.5 ppm .
hrms - esi calcd for c23h28no4 [ m + h ] : 382.2013 ; 
 found : 382.2022 .
obtained using catalyst a ( 2.3 mg , 2.94 mol ) , enyne 1c ( 0.15 ml , 1.0 m 
 in dry ch2cl2 , 0.15 mmol ) , and quinolin-8-amine 
 ( 21 mg , 0.15 mmol ) as the nucleophile in ch2cl2 ( 0.8 ml ) according to general procedure i. preparative tlc ( c - hexane / etoac 
 5:1 ) yielded 45 mg ( 81% ) of the aminated product as a pale yellow 
 oil .
h nmr ( 400 mhz , cdcl3 )  8.71 ( dd , j = 4.0 , 1.6 hz , 1h ) , 
 8.05 ( dd , j = 8.4 , 1.6 hz , 1h ) , 7.387.33 
 ( m , 2h ) , 7.05 ( d , j = 8.0 hz , 1h ) , 6.98 ( d , j = 8.4 hz , 1h ) , 6.65 ( s , 1h ) , 5.05 ( s , 1h ) , 4.89 ( s , 1h ) , 
 3.73 ( s , 3h ) , 3.72 ( s , 3h ) , 3.593.55 ( m , 1h ) , 3.01 ( qd , j = 15.2 , 2.0 hz , 1h ) , 2.92 ( d , j = 15.2 
 hz , 1h ) , 2.66 ( ddd , j = 13.6 , 8.4 , 1.6 hz , 1h ) , 2.07 
 ( dd , j = 13.6 , 8.4 hz , 1h ) , 1.57 ( s , 3h ) , 1.53 ( s , 
 3h ) ppm .
c nmr ( 101 mhz , cdcl3 )  171.9 , 171.8 , 148.1 , 146.6 , 142.3 , 138.7 , 136.1 , 
 128.9 , 127.5 , 121.2 , 113.5 , 110.9 , 106.9 , 58.6 , 55.6 , 52.7 , 47.5 , 
 44.0 , 36.3 , 30.9 , 25.2 , 25.0 ppm .
hrms - esi calcd for 
 c22h27n2o4 [ m + h ] : 383.1965 ; found : 383.1975 . obtained using catalyst a ( 3.2 mg , 4.2 mol ) , enyne 1c ( 0.21 ml , 1.0 m 
 in dry ch2cl2 , 0.21 mmol ) , and n - methylaniline ( 0.46 ml , 0.5 m in ch2cl2 , 0.23 
 mmol ) as the nucleophile in ch2cl2 ( 0.5 ml ) 
 according to general procedure i. preparative tlc ( c - hexane / etoac 
 5:1 ) yielded 61 mg ( 85% ) of the aminated product as a colorless oil .
h nmr ( 400 mhz , cdcl3 )  7.257.23 ( m , 2h ) , 7.197.14 ( m , 2h ) , 7.137.08 
 ( m , 1h ) , 5.14 ( br s , 1h ) , 5.08 ( br s , 1h ) , 3.75 ( s , 3h ) , 3.73 ( s , 
 3h ) , 3.103.05 ( m , 1h ) , 2.972.84 ( m , 2h ) , 2.73 ( s , 
 3h ) , 2.63 ( ddd , j =   13.8 , 8.6 , 1.7 hz , 1h ) , 2.21 
 ( dd , j =   13.8 , 9.3 hz , 1h ) , 1.08 ( s , 3h ) , 0.89 ( s , 
 3h ) ppm .
c nmr ( 101 mhz , cdcl3 )  171.9 , 171.8 , 150.9 , 148.9 , 128.3 , 128.0 , 124.1 , 
 110.8 , 60.0 , 58.4 , 52.7 , 48.8 , 44.0 , 36.6 , 36.3 , 21.5 , 20.8 ppm .
hrms - esi calcd for c20h28no4 [ m + h ] : 346.2013 ; found : 346.2015 . obtained using catalyst a ( 11 mg , 15.0 mol ) , enyne 1c ( 0.29 ml , 1.0 m 
 in dry ch2cl2 , 0.29 mmol ) , and n - allylaniline ( 70 mg , 0.29 mmol ) as the nucleophile in ch2cl2 ( 1.5 ml ) according to general procedure i. flash column 
 chromatography ( c - hexane / etoac 5:1 ) yielded 54 mg ( 49% ) of the aminated 
 product as a colorless solid .
h nmr ( 400 mhz , cdcl3 )  7.25 ( t , j = 
 8.0 hz , 2h ) , 7.16 ( d , j = 8.0 hz , 2h ) , 7.11 ( t , j = 8.0 hz , 1h ) , 5.665.58 ( m , 1h ) , 5.16 ( s , 1h ) , 
 5.11 ( s , 1h ) , 4.98 ( dd , j = 17.5 , 1.5 hz , 1h ) , 4.85 
 ( dd , j = 17.5 , 1.5 hz , 1h ) , 3.79 ( s , 3h ) , 3.773.76 
 ( m , 3h + 2h ) , 3.133.07 ( m , 1h ) , 2.962.87 ( m , 2h ) , 
 2.66 ( ddd , j = 14.0 , 8.5 , 1.5 hz , 1h ) , 2.30 ( dd , j = 13.5 , 9.0 hz , 1h ) , 1.11 ( s , 3h ) , 0.88 ( s , 3h ) ppm .
c nmr ( 101 mhz , cdcl3 )  172.2 , 172.1 , 149.1 , 147.9 , 137.2 , 130.0 , 127.9 , 124.8 , 
 115.7 , 110.9 , 60.4 , 58.5 , 52.7 , 52.6 , 50.6 , 49.2 , 44.1 , 36.7 , 22.2 , 
 21.9 ppm .
hrms - esi calcd for c22h30no4 [ m + h ] : 372.2169 ; found : 
 372.2156 .
mp 7577 c . obtained using catalyst a ( 11 mg , 15.0 mol ) , enyne 1c ( 0.29 ml , 1.0 m 
 in dry ch2cl2 , 0.29 mmol ) , and indoline ( 0.29 
 ml , 1.0 m in dry ch2cl2 , 0.29 mmol ) as the nucleophile 
 in ch2cl2 ( 1.5 ml ) according to general procedure 
 i. flash column chromatography ( c - hexane / etoac 5:1 ) yielded 92 mg 
 ( 87% ) of the aminated product as a colorless oil .
h nmr ( 400 mhz , cdcl3 )  7.06 
 ( dd , j = 7.5 , 0.5 hz , 1h ) , 7.01 ( t , j = 8.0 hz , 1h ) , 6.80 ( d , j = 8.0 hz , 1h ) , 6.63 ( dd , j = 7.5 , 0.5 hz , 1h ) , 5.07 ( br s , 2h ) , 3.76 ( s , 3h ) , 3.75 
 ( s , 3h ) , 3.60 ( t , j = 10.0 hz , 1h ) , 3.523.41 
 ( m , 2h ) , 2.93 ( br s , 2h ) , 2.88 ( t , j = 8.5 hz , 2h ) , 
 2.63 ( ddd , j = 13.5 , 8.5 , 1.5 hz , 1h ) , 2.10 ( dd , j = 13.5 , 9.0 hz , 1h ) , 1.37 ( s , 3h ) , 1.27 ( s , 3h ) ppm .
c nmr ( 101 mhz , cdcl3 )  172.0 , 171.9 , 149.8 , 148.5 , 131.6 , 126.9 , 124.4 , 116.6 , 
 110.6 , 109.8 , 58.7 , 58.3 , 52.8 , 52.7 , 49.6 , 48.5 , 44.0 , 36.2 , 28.1 , 
 21.4 , 21.0 ppm .
hrms - esi calcd for c21h28no4 [ m + h ] : 358.2013 ; 
 found : 358.2025 .
obtained using catalyst a ( 11 mg , 15.0 mol ) , enyne 1c ( 0.29 ml , 1.0 m 
 in dry ch2cl2 , 0.29 mmol ) , and 1,2,3,4-tetrahydroquinoline 
 ( 0.29 ml , 1.0 m in dry ch2cl2 , 0.29 mmol ) as 
 the nucleophile in ch2cl2 ( 1.5 ml ) according 
 to general procedure i. washing with 10% aqueous solution of naoh 
 to remove excess 1,2,3,4-tetrahydroquinoline , flash column chromatography 
 ( c - hexane / etoac 5:1 ) , and subsequent preparative tlc ( ch2cl2/c - hexane 1:2 ) yielded 56 mg ( 51% ) of the aminated 
 product as a colorless oil .
h nmr ( 400 mhz , cdcl3 )  7.067.04 ( m , 2h ) , 7.01 
 ( d , j = 7.5 hz , 1h ) , 6.74 ( dt , j = 6.5 , 2.5 hz , 1h ) , 5.06 ( s , 1h ) , 4.98 ( s , 1h ) , 3.75 ( s , 3h ) , 3.72 
 ( s , 3h ) , 3.62 ( dt , j = 10.0 , 2.0 hz , 1h ) , 3.333.28 
 ( m , 1h ) , 3.233.18 ( m , 1h ) , 2.972.89 ( m , 2h ) , 2.65 
 ( t , j = 6.5 hz , 2h ) , 2.55 ( ddd , j = 13.6 , 8.0 , 1.5 
 hz , 1h ) , 2.06 ( dd , j = 13.5 , 9.5 hz , 1h ) , 1.89 ( quin , j = 6.5 hz , 2h ) , 1.43 ( s , 3h ) , 1.32 ( s , 3h ) ppm .
c nmr ( 101 mhz , cdcl3 )  
 172.1 , 171.9 , 148.9 , 145.9 , 131.1 , 128.4 , 125.4 , 119.8 , 118.3 , 110.5 , 
 60.8 , 58.4 , 52.8 , 52.7 , 48.8 , 44.3 , 44.1 , 36.6 , 28.0 , 25.3 , 24.3 , 
 23.6 ppm .
hrms - esi calcd for c22h30no4 [ m + h ] : 372.2169 ; found : 
 372.2162 . obtained using catalyst a ( 4.6 mg , 0.006 mmol ) , enyne 1d ( 81 mg , 0.30 mmol ) , 
 and 4-bromoaniline ( 57 mg , 0.33 mmol ) as the nucleophile in ch2cl2 ( 0.9 ml )
according to general procedure i ( stirred 
 vigorously at rt for 5 h ) .
purification by column chromatography ( pentane / et2o 95:5 to 9:1 ) yielded 125 mg of colorless gum ( 94% , contains 
 ca .
35% impurities ) that was further crystallized from 0.4 
 ml of diethyl ether layered with 1.2 ml of pentane ( sonication initiated 
 the crystallization ) to yield 110 mg of colorless crystals ( 84% ) .
d , j =   4.3 hz , 4h ) , 7.25 ( ddd , j =   8.7 , 4.9 , 3.9 hz , 1h ) , 7.177.12 ( m , 2h ) , 6.406.35 
 ( m , 2h ) , 5.07 ( br s , 1h ) , 4.77 ( q , j =   2.1 hz , 1h ) , 
 4.43 ( d , j =   5.2 hz , 1h ) , 4.02 ( br s , 1h ) , 3.72 
 ( d , j =   11.2 hz , 1h ) , 3.66 ( d , j =   11.4 hz , 1h ) , 3.553.48 ( m , 2h ) , 2.99 ( dddt , j = 10.6 , 7.9 , 5.2 , 2.2 hz , 1h ) , 2.53 ( dq , j = 16.5 , 
 1.6 hz , 1h ) , 2.18 ( dq , j = 16.4 , 2.4 hz , 1h ) , 1.67 
 ( dd , j = 13.6 , 8.2 hz , 1h ) , 1.50 ( dd , j = 13.6 , 10.3 hz , 1h ) , 1.40 ( s , 3h ) , 1.38 ( s , 3h ) ppm
. c nmr ( 126 mhz , cdcl3 )  
 149.0 , 146.7 , 141.7 , 131.7 , 128.5 , 127.2 , 126.8 , 115.5 , 109.5 , 109.5 , 
 97.9 , 69.4 , 67.5 , 59.9 , 48.8 , 41.7 , 39.4 , 34.0 , 24.7 , 22.8 ppm .
hrms - esi calcd for c24h28brno2na [ m + na ] : 464.1196 ; found : 464.1197 .
mp 110112 c . obtained using catalyst a ( 3.9 mg , 0.005 mmol ) , enyne 1f ( 64.6 mg , 0.25 mmol ) , 
 and 4-bromoaniline ( 47 mg , 0.275 mmol ) as the nucleophile in ch2cl2 ( 1.0 ml ) according to general procedure i ( stirred 
 vigorously at r.t . for 5 h ) .
purification by column chromatography 
 ( pentane / et2o 95:5 to 85:15 ) yielded 80 mg ( 74% ) of the 
 aminated product as a colorless oil .
h nmr ( 500 mhz , cdcl3 )  7.357.28 
 ( m , 4h ) , 7.257.20 ( m , 1h ) , 7.157.11 ( m , 2h ) , 6.376.32 
 ( m , 2h ) , 4.98 ( q , j = 2.1 hz , 1h ) , 4.75 ( q , j =   2.1 hz , 1h ) , 4.504.46 ( m , 2h ) , 3.41 ( s , 3h ) , 
 3.32 ( s , 2h ) , 3.27 ( s , 3h ) , 3.12 ( s , 2h ) , 3.02 ( t , j = 8.2 hz , 1h ) , 2.40 ( dq , j = 16.3 , 2.3 hz , 1h ) , 
 2.31 ( d , j = 16.2 hz , 1h ) , 1.75 ( dd , j = 13.9 , 9.1 hz , 1h ) , 1.51 ( dd , j = 13.9 , 9.3 hz , 
 1h ) ppm .
c nmr ( 126 mhz , cdcl3 )  151.2 , 147.0 , 142.3 , 131.6 , 128.5 , 126.9 , 126.7 , 
 115.1 , 108.7 , 107.7 , 77.7 , 76.2 , 60.4 , 59.3 , 59.3 , 49.7 , 45.4 , 40.5 , 
 32.2 ppm .
hrms - esi calcd for c23h28brno2na [ m + na ] : 452.1196 ; found : 
 452.1197 . obtained using catalyst a ( 2.0 mg , 0.0026 mmol ) , enyne 1e ( 61 mg , 0.13 mmol ) , 
 and 4-bromoaniline ( 57 mg , 0.143 mmol ) as the nucleophile in ch2cl2 ( 0.6 ml ) according to general procedure i ( stirred 
 vigorously at rt for 5 h ) .
purification by column chromatography ( pentane / et2o 95:5 to 85:15 ) yielded 61 mg ( 73% ) of the aminated product 
 as a colorless oil .
h nmr ( 500 
 mhz , cdcl3 )  7.347.21 ( m , 7h ) , 7.187.13 
 ( m , 2h ) , 7.107.06 ( m , 2h ) , 6.926.88 ( m , 2h ) , 6.876.83 
 ( m , 2h ) , 6.206.15 ( m , 2h ) , 4.97 ( q , j = 2.1 
 hz , 1h ) , 4.74 ( q , j =   2.1 hz , 1h ) , 4.49 ( s , 2h ) , 
 4.47 ( t , j 3.0 hz , 1h ) , 4.37 ( s , 2h ) , 4.34 ( br s , 
 1h ) , 3.83 ( s , 3h ) , 3.82 ( s , 3h ) , 3.463.39 ( m , 2h ) , 3.233.17 
 ( m , 2h ) , 2.99 ( dddt , j = 9.3 , 6.9 , 4.5 , 2.2 hz , 1h ) , 
 2.46 ( dq , j = 16.4 , 2.3 hz , 1h ) , 2.35 ( d , j = 16.2 hz , 1h ) , 1.78 ( dd , j = 14.0 , 9.2 
 hz , 1h ) , 1.52 ( dd , j = 13.9 , 9.3 hz , 1h ) ppm .
c nmr ( 126 mhz , cdcl3 )  159.2 , 159.0 , 151.5 , 146.9 , 142.3 , 131.5 , 130.6 , 129.3 , 
 128.9 , 128.4 , 126.9 , 126.6 , 115.1 , 113.8 , 113.7 , 108.7 , 107.5 , 74.9 , 
 73.3 , 73.1 , 72.8 , 60.3 , 55.3 , 55.2 , 49.7 , 45.5 , 40.6 , 32.1 ppm .
hrms - esi calcd for c37h40brno4na [ m + na ] : 664.2033 ; found : 664.2030 .
a solution of compound 4e ( 40 
 mg , 0.08 mmol ) in degassed dmf ( 0.5 ml ) was treated with pd(oac)2 ( 1.8 mg , 8 mol ) , pph3 ( 4.2 mg , 16 mol ) , 
 and k2co3 ( 22 mg , 0.16 mmol ) under a n2 atmosphere , and the solution was heated at 110 c for 7 h. 
 purification by flash column chromatography ( pentane / et2o 9:1 ) provided product 5e ( 20 mg , 67% ) as a colorless 
 oil .
h nmr ( 500 mhz , cdcl3 )  8.128.07 ( m , 2h ) , 7.547.45 ( m , 4h ) , 
 7.38 ( dd , j = 7.5 , 1.6 hz , 1h ) , 7.28 ( td , j = 7.5 , 1.6 hz , 1h ) , 7.23 ( td , j = 7.4 , 
 1.5 hz , 1h ) , 3.79 ( s , 3h ) , 3.50 ( s , 3h ) , 3.45 ( d , j = 14.2 hz , 1h ) , 3.31 ( dd , j = 12.4 , 7.8 hz , 1h ) , 
 2.66 ( dd , j = 13.8 , 7.8 hz , 1h ) , 2.54 ( d , j = 14.2 hz , 1h ) , 2.17 ( dd , j = 13.8 , 12.4 
 hz , 1h ) , 1.20 ( s , 3h ) ppm . c nmr ( 126 mhz , cdcl3 )  173.4 , 171.4 , 165.8 , 142.4 , 
 138.7 , 131.7 , 130.8 , 128.8 , 128.6 , 127.9 , 127.7 , 127.0 , 125.7 , 58.5 , 
 53.2 , 52.9 , 46.9 , 46.5 , 44.5 , 38.8 , 28.7 ppm .
hrms - esi calcd for c23h24no4 [ m + h ] : 378.1700 ; found : 378.1697 .
a solution of compound 4f ( 60 mg , 
 0.11 mmol ) in degassed dmf ( 0.7 ml ) was treated with pd(oac)2 ( 2.3 mg , 10 mol ) , pph3 ( 5.4 mg , 21 mol ) , 
 and k2co3 ( 28 mg , 0.21 mmol ) under a n2 atmosphere , and the solution was heated at 110 c for 4 h. 
 purification by flash column chromatography ( pentane / et2o 9:1 ) provided product 5f ( 34 mg , 73% ) as a colorless 
 oil .
h nmr ( 500 mhz , cdcl3 )  8.158.04 ( m , 2h ) , 7.527.45 ( m , 4h ) , 
 7.427.35 ( m , 2h ) , 3.78 ( s , 3h ) , 3.58 ( s , 3h ) , 3.33 ( d , j = 14.3 hz , 1h ) , 3.28 ( dd , j = 12.2 , 8.1 
 hz , 1h ) , 2.63 ( dd , j = 13.9 , 8.1 hz , 1h ) , 2.58 ( d , j = 14.3 hz , 1h ) , 2.21 ( dd , j = 13.9 , 12.2 
 hz , 1h ) , 1.20 ( s , 3h ) ppm . c nmr ( 126 mhz , cdcl3 )  173.1 , 171.2 , 166.4 , 141.6 , 
 138.3 , 133.9 , 131.1 , 130.9 , 130.2 , 128.8 , 128.8 , 127.0 , 120.9 , 58.5 , 
 53.3 , 53.1 , 46.8 , 46.1 , 44.7 , 38.9 , 28.4 ppm .
hrms - esi calcd for c23h23brno4 [ m + h ] : 456.0805 ; found : 456.0798 .
a solution of compound 4 g ( 60 
 mg , 0.11 mmol ) in degassed dmf ( 0.75 ml ) was treated with pd(oac)2 ( 2.5 mg , 11 mol ) , pph3 ( 5.8 mg , 22 mol ) , 
 and k2co3 ( 31 mg , 0.22 mmol ) under a n2 atmosphere , and the solution was heated at 110 c for 4 h. 
 purification by flash column chromatography ( pentane / et2o 9:1 ) provided product 5 g ( 33 mg , 72% ) as a colorless 
 oil .
h nmr ( 500 mhz , cdcl3 )  8.128.06 ( m , 2h ) , 7.577.44 ( m , 4h ) , 
 7.31 ( d , j = 8.2 hz , 1h ) , 7.20 ( dd , j = 8.2 , 2.3 hz , 1h ) , 3.79 ( s , 3h ) , 3.53 ( s , 3h ) , 3.42 ( d , j = 14.3 hz , 1h ) , 3.32 ( dd , j = 12.4 , 7.7 
 hz , 1h ) , 2.68 ( dd , j = 13.8 , 7.7 hz , 1h ) , 2.50 ( d , j = 14.4 hz , 1h ) , 2.10 ( dd , j = 13.8 , 12.4 
 hz , 1h ) , 1.18 ( s , 3h ) ppm . c nmr ( 126 mhz , cdcl3 )  173.2 , 171.3 , 167.3 , 143.7 , 
 138.2 , 133.0 , 131.2 , 130.3 , 128.8 , 128.4 , 127.6 , 127.1 , 127.0 , 58.4 , 
 53.3 , 53.0 , 46.7 , 46.4 , 44.4 , 38.9 , 28.6 ppm .
hrms - esi calcd for c23h23clno4 [ m + h ] : 412.1310 ; found : 412.1320 .
a dry 10 ml mw vial was charged with pdcl2(pph3)2 ( 56 mg , 0.079 mmol ) , cui ( 38 
 mg , 0.20 mmol ) , and 2-iodoaniline 4e ( 500 mg , 0.99 mmol ) , 
 and the mw vial was sealed and left under argon .
degassed et3n ( 7 ml ) and degassed dmf ( 3 ml ) were added followed by trimethylsilylacetylene 
 ( 0.68 ml , 4.95 mmol , 5 equiv ) at 25 c .
the resulting mixture 
 was stirred at 25 c for 1.5 h ( complete conversion monitored 
 by gc - ms ) .
the dark brown mixture was partitioned between water ( 50 
 ml ) and diethyl ether ( 20 ml ) .
the aqueous layer was re - extracted 
 with diethyl ether ( 2  20 ml ) .
the title product 
 was obtained after purification by chromatography on silica gel eluting 
 with pentane / et2o 9:1 to 4:1 as a pale brown crystalline 
 solid ( 451 mg , 96% ) .
h nmr ( 500 
 mhz , cdcl3 )  7.387.22 ( m , 6h ) , 6.99 ( ddd , j = 8.6 , 7.4 , 1.6 hz , 1h ) , 6.56 ( td , j = 
 7.5 , 1.0 hz , 1h ) , 6.30 ( d , j = 8.3 hz , 1h ) , 5.14 
 ( d , j = 4.9 hz , 1h ) , 5.08 ( q , j = 
 2.6 hz , 1h ) , 4.72 ( q , j = 2.5 hz , 1h ) , 4.51 ( t , j = 5.4 hz , 1h ) , 3.70 ( s , 3h ) , 3.70 ( s , 3h ) , 3.183.10 
 ( m , 1h ) , 3.04 ( dq , j = 16.4 , 1.6 hz , 1h ) , 2.95 ( dq , j = 16.5 , 2.6 hz , 1h ) , 2.43 ( ddd , j = 13.6 , 
 7.8 , 1.7 hz , 1h ) , 2.22 ( dd , j = 13.5 , 10.4 hz , 1h ) , 
 0.30 ( s , 9h ) ppm .
c nmr ( 126 
 mhz , cdcl3 )  171.7 , 171.4 , 148.6 , 146.6 , 141.5 , 
 132.1 , 129.9 , 128.5 , 127.2 , 126.9 , 116.6 , 111.1 , 110.0 , 108.0 , 102.0 , 
 100.2 , 59.8 , 58.0 , 52.8 , 52.7 , 49.3 , 41.8 , 35.4 ,  0.1 ppm .
hrms - esi calcd for c28h34no4si [ m + h ] : 476.2252 ; found : 476.2247 .
according to the procedure for 6e , with 4f ( 440 mg , 0.753 mmol ) , pdcl2(pph3)2 ( 42 mg , 0.06 mmol ) , and cui ( 29 mg , 
 0.15 mmol ) in degassed dfm / et3n ( 1:2 , 6.75 ml ) to which 
 was added tms - acetylene ( 208 l , 1.51 mmol , 2 equiv ) , followed 
 by stirring at 25 c for 1.5 h. obtained as a pale yellow oil 
 after purification by column chromatography on silica gel eluting 
 with pentane / et2o 9:1 to 4:1 ( 400 mg , 96% ) .
h nmr ( 500 mhz , cdcl3 )  
 7.387.31 ( m , 4h ) , 7.307.24 ( m , 1h ) , 7.19 ( d , j = 8.2 hz , 1h ) , 6.53 ( dd , j = 8.2 , 2.0 
 hz , 1h ) , 6.29 ( d , j = 1.9 hz , 1h ) , 5.19 ( d , j = 5.3 hz , 1h ) , 5.07 ( dq , j = 2.5 , 1.5 
 hz , 1h ) , 4.714.68 ( m , 1h ) , 4.48 ( t , j = 5.6 
 hz , 1h ) , 3.70 ( s , 3h ) , 3.69 ( s , 3h ) , 3.193.09 ( m , 1h ) , 3.02 
 ( dq , j = 16.4 , 1.6 hz , 1h ) , 2.91 ( dq , j = 16.5 , 2.6 hz , 1h ) , 2.43 ( ddd , j = 13.5 , 7.8 , 
 1.7 hz , 1h ) , 2.16 ( dd , j = 13.5 , 10.4 hz , 1h ) , 0.31 
 ( s , 9h ) ppm .
c nmr ( 126 mhz , 
 cdcl3 )  171.7 , 171.4 , 149.4 , 146.5 , 140.7 , 135.7 , 
 132.9 , 128.6 , 127.5 , 126.8 , 116.7 , 111.1 , 110.2 , 106.6 , 101.2 , 100.9 , 
 59.7 , 58.0 , 52.8 , 52,8 , 49.1 , 41.8 , 35.8 , 0.0 ppm .
hrms - esi calcd for c28h32brno4sina [ m + na ] : 576.1176 ; found : 576.1196 .
prepared according to the procedure for 6e , with 4 g ( 550 mg , 1.02 mmol ) , pdcl2(pph3)2 ( 57.2 mg , 0.08 mmol ) , cui ( 39 mg , 0.20 
 mmol ) in degassed dfm / et3n ( 1:2 , 7.5 ml ) to which was added 
 tms - acetylene ( 282 l , 2.04 mmol , 2 equiv ) , followed by stirring 
 at 25 c for 1.5 h. obtained as a yellow oil after purification 
 by column chromatography on silica gel eluting with pentane / et2o 9:1 to 4:1 ( 502 mg , 97% ) .
h nmr ( 500 mhz , cdcl3 )  7.39 ( d , j = 2.4 hz , 1h ) , 7.367.30 ( m , 4h ) , 7.287.23 
 ( m , 1h ) , 7.05 ( dd , j = 8.8 , 2.3 hz , 1h ) , 6.16 ( d , j = 8.8 hz , 1h ) , 5.11 ( d , j = 4.8 hz , 1h ) , 
 5.08 ( q , j = 2.5 hz , 1h ) , 4.71 ( q , j = 2.5 hz , 1h ) , 4.47 ( t , j = 5.3 hz , 1h ) , 3.70 ( s , 
 3h ) , 3.69 ( s , 3h ) , 3.13 ( dddd , j = 10.4 , 8.0 , 5.6 , 
 2.3 hz , 1h ) , 3.03 ( dq , j = 16.5 , 1.6 hz , 1h ) , 2.92 
 ( dq , j = 16.5 , 2.6 hz , 1h ) , 2.40 ( ddd , j = 13.6 , 7.8 , 1.7 hz , 1h ) , 2.18 ( dd , j = 13.5 , 10.5 
 hz , 1h ) , 0.30 ( s , 9h ) ppm .
c nmr ( 126 mhz , cdcl3 )  171.7 , 171.4 , 147.5 , 146.5 , 
 140.9 , 134.2 , 132.5 , 128.6 , 127.4 , 126.8 , 112.7 , 110.1 , 110.0 , 107.8 , 
 101.7 , 100.3 , 59.8 , 58.0 , 52.8 , 52,8 , 49.2 , 41.8 , 35.7 , 0.0 ppm .
hrms - esi calcd for c28h32clno4sina [ m + na ] : 532.1681 ; found : 532.1693 .
substrate 6e ( 150 mg , 0.32 
 mmol ) was suspended in methanol ( 1 ml ) at 25 c , and k2co3 ( 131 mg , 0.95 mmol ) was added .
the mixture was stirred 
 vigorously at 25 c for 3 h ( disappearance of starting material 
 monitored by gc - ms ) .
the volatiles were then removed under a stream 
 of nitrogen , and the residue was purified by column chromatography 
 on silica gel eluting with pentane / et2o 4:1 to afford 120 
 mg of colorless oil ( 94% ) . note : alternatively 
 the deprotection of the tms group can be carried out on the crude 
 mixture after sonogashira coupling to afford the title alkyne in 81% 
 yield over 2 steps ( 1 g scale of iodoaniline substrate [ 1.98 mmol ] , 
 650 mg [ 1.61 mmol ] of alkyne obtained ) .
h nmr ( 500 mhz , cdcl3 )  7.387.29 
 ( m , 5h ) , 7.277.22 ( m , 1h ) , 7.03 ( ddd , j = 
 8.6 , 7.4 , 1.6 hz , 1h ) , 6.58 ( td , j = 7.5 , 1.0 hz , 
 1h ) , 6.31 ( d , j = 8.4 hz , 1h ) , 5.14 ( d , j = 5.1 hz , 1h ) , 5.07 ( q , j = 2.1 hz , 1h ) , 4.73 ( q , j = 2.1 hz , 1h ) , 4.55 ( t , j = 5.4 hz , 1h ) , 
 3.72 ( s , 3h ) , 3.70 ( s , 3h ) , 3.52 ( s , 1h ) , 3.223.13 ( m , 1h ) , 
 3.082.96 ( m , 2h ) , 2.45 ( dd , j = 13.7 , 8.2 
 hz , 1h ) , 2.26 ( dd , j = 13.7 , 9.9 hz , 1h ) ppm .
c nmr ( 126 mhz , cdcl3 )  171.8 , 171.7 , 148.8 , 147.0 , 141.4 , 132.3 , 130.1 , 128.5 , 
 127.2 , 126.8 , 116.5 , 111.0 , 110.0 , 106.8 , 83.2 , 80.7 , 60.0 , 58.2 , 
 52.8 , 49.3 , 42.1 , 35.4 ppm .
hrms - esi calcd for c25h25no4na [ m + na ] : 426.1676 ; found : 426.1681 .
prepared according to the procedure for 7e , with 6f ( 115 mg , 0.21 mmol ) and k2co3 ( 86 mg , 0.62 mmol ) in methanol ( 0.7 ml ) , followed 
 by stirring at 25 c for 1.5 h. obtained as a colorless oil after 
 purification by column chromatography on silica gel eluting with pentane / et2o 9:1 to 4:1 ( 72 mg , 72% ) .
h nmr ( 500 mhz , cdcl3 )  7.41 ( d , j = 2.4 hz , 1h ) , 7.357.29 ( m , 4h ) , 7.277.23 
 ( m , 1h ) , 7.09 ( dd , j = 8.8 , 2.4 hz , 1h ) , 6.17 ( d , j = 8.9 hz , 1h ) , 5.13 ( d , j = 5.1 hz , 1h ) , 
 5.07 ( q , j = 2.1 hz , 1h ) , 4.71 ( q , j = 2.1 hz , 1h ) , 4.49 ( t , j = 5.4 hz , 1h ) , 3.72 ( s , 
 3h ) , 3.70 ( s , 3h ) , 3.54 ( s , 1h ) , 3.193.12 ( m , 1h ) , 3.052.95 
 ( m , 2h ) , 2.42 ( dd , j = 13.7 , 8.2 hz , 1h ) , 2.21 ( dd , j = 13.8 , 9.8 hz , 1h ) ppm .
c nmr ( 126 mhz , cdcl3 )  171.7 , 171.7 , 147.8 , 
 146.9 , 140.9 , 134.4 , 132.9 , 128.6 , 127.4 , 126.7 , 112.6 , 110.0 , 108.7 , 
 107.7 , 84.3 , 79.2 , 60.0 , 58.1 , 52.9 , 52.8 , 49.2 , 42.2 , 35.4 ppm .
hrms - esi calcd for c25h24brno4na [ m + na ] : 504.0781 ; found : 504.0778 .
prepared according to the procedure for 7e , with 6 g ( 135 mg , 0.27 mmol ) and k2co3 ( 110 mg , 0.79 mmol ) in methanol ( 1 ml ) , followed by 
 stirring at 25 c for 2.5 h. obtained as a pale yellow oil after 
 purification by column chromatography on silica gel eluting with pentane / et2o 9:1 to 4:1 ( 78 mg , 67% ) .
h nmr ( 500 mhz , cdcl3 )  7.367.31 
 ( m , 4h ) , 7.297.24 ( m , 1h ) , 7.22 ( d , j = 8.1 
 hz , 1h ) , 6.55 ( dd , j = 8.2 , 2.0 hz , 1h ) , 6.29 ( d , j = 1.9 hz , 1h ) , 5.21 ( d , j = 5.5 hz , 1h ) , 
 5.07 ( q , j = 2.1 hz , 1h ) , 4.71 ( q , j = 2.1 hz , 1h ) , 4.51 ( t , j = 5.6 hz , 1h ) , 3.72 ( s , 
 3h ) , 3.70 ( s , 3h ) , 3.54 ( s , 1h ) , 3.203.12 ( m , 1h ) , 3.042.94 
 ( m , 2h ) , 2.44 ( dd , j = 13.7 , 8.3 hz , 1h ) , 2.20 ( dd , j = 13.8 , 9.8 hz , 1h ) ppm .
c nmr ( 126 mhz , cdcl3 )  171.7 , 171.7 , 149.6 , 
 146.8 , 140.6 , 136.0 , 133.1 , 128.7 , 127.5 , 126.7 , 116.7 , 111.0 , 110.1 , 
 105.3 , 84.0 , 79.8 , 59.9 , 58.2 , 52.8 , 49.2 , 42.2 , 35.4 ppm .
hrms - esi calcd for c25h24clno4na [ m + na ] : 460.1286 ; found : 460.1286 . in a dry vial , 7e ( 100 mg , 
 0.25 mmol )
was dissolved in dry ch2cl2 ( 2.5 
 ml ) and iprauntf2 ( d2 ) ( 10.7 mg , 12 mol ) was added in one portion .
the mixture 
 was stirred at 25 c for 8 h ( monitored by gc - ms ) .
the solvent 
 was removed under a stream of nitrogen , and the crude mixture was 
 loaded on silica gel and purified by column chromatography on silica 
 gel eluting with pentane / et2o 9:1 to 4:1 to afford the 
 title product as a colorless solid ( 78 mg , 78% ) .
h nmr ( 500 mhz , cdcl3 )  7.62 
 ( d , j = 7.9 hz , 1h ) , 7.477.42 ( m , 2h ) , 7.407.34 
 ( m , 2h ) , 7.327.18 ( m , 4h ) , 7.09 ( ddd , j = 
 7.9 , 7.0 , 1.0 hz , 1h ) , 6.60 ( d , j = 3.2 hz , 1h ) , 
 5.29 ( d , j = 11.0 hz , 1h ) , 4.90 ( q , j = 2.0 hz , 1h ) , 4.184.14 ( m , 1h ) , 3.873.78 ( m , 1h ) , 
 3.75 ( s , 3h ) , 3.63 ( s , 3h ) , 3.23 ( dq , j = 16.3 , 2.4 
 hz , 1h ) , 2.97 ( dq , j = 16.3 , 1.5 hz , 1h ) , 2.66 ( ddd , j = 13.9 , 7.9 , 1.6 hz , 1h ) , 1.88 ( dd , j = 13.8 , 8.2 hz , 1h ) ppm .
c nmr ( 126 mhz , cdcl3 )  171.9 , 171.7 , 146.7 , 139.8 , 
 136.4 , 128.4 , 128.3 , 127.8 , 127.6 , 124.6 , 121.7 , 120.9 , 119.6 , 111.6 , 
 109.7 , 102.5 , 63.4 , 58.1 , 52.9 , 52.8 , 46.3 , 41.7 , 38.4 ppm .
hrms - esi calcd for c25h26no4 [ m + h ] : 404.1856 ; found : 404.1853 .
according to the procedure for 8e , with 7f ( 61 mg , 0.13 mmol ) and iprauntf2 ( d2 ) ( 5.5 mg , 6.3 mol ) 
 in ch2cl2 ( 1.2 ml ) , followed by stirring at 
 25 c for 8 h. obtained as a colorless foamy solid after purification 
 by column chromatography on silica gel eluting with pentane / et2o 9:1 to 4:1 ( 47 mg , 77% ) .
h nmr ( 500 mhz , cdcl3 )  7.71 ( d , j = 1.6 hz , 1h ) , 7.40 ( d , j = 3.3 hz , 1h ) , 
 7.347.21 ( m , 7h ) , 6.51 ( d , j = 3.5 hz , 1h ) , 
 5.22 ( d , j = 10.9 hz , 1h ) , 4.89 ( q , j = 1.9 hz , 1h ) , 4.16 ( q , j = 1.7 hz , 1h ) , 3.813.74 
 ( m , 1h ) , 3.73 ( s , 3h ) , 3.63 ( s , 3h ) , 3.19 ( dq , j = 
 16.3 , 2.3 hz , 1h ) , 2.96 ( dq , j = 16.4 , 1.5 hz , 1h ) , 
 2.59 ( ddd , j = 13.8 , 7.9 , 1.5 hz , 1h ) , 1.84 ( dd , j = 13.8 , 8.2 hz , 1h ) ppm .
c nmr ( 126 mhz , cdcl3 )  171.8 , 171.7 , 146.6 , 
 139.4 , 135.0 , 130.0 , 128.6 , 128.1 , 127.5 , 125.9 , 124.5 , 123.4 , 112.9 , 
 111.7 , 111.2 , 102.1 , 63.7 , 58.0 , 52.9 , 52.9 , 46.3 , 41.6 , 38.3 ppm .
hrms - esi calcd for c25h25brno4 [ m + h ] : 482.0961 ; found : 482.0959 .
according to the procedure for 8e , with 7 g ( 62 mg , 0.14 mmol ) and iprauntf2 ( d2 ) ( 6.1 mg , 7.1 mol ) 
 in ch2cl2 ( 1.3 ml ) , followed by stirring at 
 25 c for 8 h. obtained as a colorless foamy solid after purification 
 by column chromatography on silica gel eluting with pentane / et2o 9:1 to 4:1 ( 42 mg , 68% ) .
h nmr ( 500 mhz , cdcl3 )  7.49 ( d , j = 8.4 hz , 1h ) , 7.417.39 ( m , 2h ) , 7.367.33 
 ( m , 2h ) , 7.327.28 ( m , 2h ) , 7.277.22 ( m , 1h ) , 7.04 
 ( dd , j = 8.4 , 1.8 hz , 1h ) , 6.55 ( dd , j = 3.3 , 1.8 hz , 1h ) , 5.18 ( d , j = 11.0 hz , 1h ) , 
 4.89 ( q , j = 2.0 hz , 1h ) , 4.14 ( dd , j = 2.7 , 1.5 hz , 1h ) , 3.813.75 ( m , 1h ) , 3.74 ( s , 3h ) , 3.64 
 ( s , 3h ) , 3.20 ( dq , j = 16.4 , 2.4 hz , 1h ) , 2.96 ( dq , j = 16.3 , 1.5 hz , 1h ) , 2.61 ( ddd , j = 13.8 , 
 7.9 , 1.6 hz , 1h ) , 1.83 ( dd , j = 13.8 , 8.2 hz , 1h ) 
 ppm .
c nmr ( 126 mhz , cdcl3 )  171.8 , 171.6 , 146.5 , 139.4 , 136.8 , 128.6 , 128.1 , 
 127.8 , 127.6 , 126.8 , 125.3 , 121.7 , 120.3 , 111.7 , 109.7 , 102.8 , 63.6 , 
 58.1 , 52.9 , 52.9 , 46.3 , 41.6 , 38.3 ppm .
hrms - esi calcd 
 for c25h24clno4na [ m 
 + na ] : 460.1286 ; found : 460.1281 .
 a practical aminocyclization of 1,6-enynes 
 with a wide variety 
 of substituted anilines , including n - alkyl anilines , 
 has been achived by using cationic [ johnphosau(mecn)]sbf6 as a general purpose catalyst . 
 the resulting adducts can be easily 
 converted into polycyclic compounds by palladium- and gold - catalyzed 
 reactions . 
Introduction
Results and Discussion
Conclusions
Experimental Section