2,1-borazaronaphthalenes serve as versatile 
 isosteres of all - carbon 
 naphthalene substructures , which allows facile emplacement of a variety 
 of substituents about the ring in an efficient and selective manner . 
 because of electronic desymmetrization brought about by the incorporation 
 of a b 
n bond in these aromatic systems , borazines have proven 
 to be far more easily elaborated than naphthalenes themselves .
previous 
 studies have focused on decorating these ring systems by utilizing 
 arylation reactions .
2-alkenylnaphthalenes 
 can be synthesized through a variety of transition - metal - catalyzed 
 transformations , including heck , mizoroki  heck , hiyama , and suzuki  miyaura reactions . however , installation of an alkenyl 
 substituent on a functionalized naphthalene is more challenging and 
 often requires four or five steps .
one 
 method to afford alkenyl - substituted naphthalenes is to perform free - radical 
 bromination of a methyl - substituted derivative followed by a wittig 
 olefination . aside from the generation 
 of a stoichiometric amount of difficult - to - remove phosphine oxide 
 waste , additional substitution on
similarly , titanium - mediated 
 carbonylation with dichloromethyl methyl ether followed by wittig 
 olefination afforded 2-alkyl-3-alkenylnaphthalene in moderate yield 
 over two steps .
in addition to the drawbacks 
 described above , the use of a strong lewis acid limits functional 
 group tolerability in this approach .
further , there is only one example 
 demonstrating the installation of an alkenyl substituent on a 2-arylnapthalene through the cross - coupling of naphthyl iodide and alkenylboronic acid , 
 which provides 2-aryl-3-alkenylnaphthalene in good yield .
the naphthyl iodide in this case was synthesized 
 through gold - catalyzed cyclization / iodination , which required preparation 
 of the requisite starting material ( 1-arylalka-2,3-dienyl acetate ) . 
 additionally , to the best of our knowledge , installation of an alkenyl 
 substituent at the c3 position of a 1,2-disubstituted naphthalene 
 has not been reported . accessing 2,1-borazaronaphthalenes ,
a 
 class of azaborines that are bn - isosteres 
 of naphthalene , with alkenyl 
 substituents at the c3 position under mild reaction conditions would 
 therefore serve as an example of how functionalized azaborines could 
 be prepared more efficiently than their corresponding all - carbon analogues . 
 recently , we reported the bromination of 2,1-borazaronaphthalenes 
 in high yield under mild reaction conditions with complete regiochemical 
 control . because of the inherent reactivity 
 of azaborine , bromination occurs selectively at the c3 position of 
 the azaborine in the presence of alkyl / aryl substituents on boron 
 and nitrogen .
miyaura 
 cross - coupling reactions with potassium 
 alkenyltrifluoroborates as a route to 
 c3-alkenyl - substituted 2,1-borazaronaphthalenes , a compound class 
 that has not been previously reported .
optimization of the reaction of 3-bromo-2-methyl-2,1-borazaronaphthalene 1 with functionalized alkenyltrifluoroborate 2 was carried out by screening palladium sources , solvents , and bases . 

side products represent the sum of homocoupling of the azaborine , 
 protodebromination of the azaborine , and unidentifiable side products . 

conditions for the cross - coupling of potassium aryltrifluoroborates with 
 brominated 2,1-borazaronaphthalenes did not afford the desired product 
 in appreciable yield ( table 1 , entry 1 ) .
therefore , several other ligands were 
 screened in this reaction ( entries 24 and 7 ) .
of the ligands 
 tested , triphenylphosphine ( pph3 ) and 1,1-bis(diphenylphosphino)ferrocene 
 ( dppf ) provided the highest conversions to products . several solvents / ratios 
 were tested for these ligands , and the best result was obtained using 
 toluene as the cosolvent and pd(dppf)cl2 as the palladium 
 source ( entry 7 ) .
a representative set of potassium 
 alkenyltrifluoroborates were 
 subjected to the developed reaction conditions with 3-bromo-2-methyl-2,1-borazaronaphthalene 
 as the electrophilic partner ( table 2 ) .
cyclic 
 alkenyltrifluoroborates were successful nucleophiles in the reaction 
 by providing the desired product in yields up to 90% ( entries 5 , 6 , 
 8 , and 10 ) .
alkenyltrifluoroborates with alkyl substituents afforded 
 the desired product in high yields ( entries 2 , 3 , and 9 ) .
vinyltrifluoroborate 
 was a suitable nucleophile for the reaction because the azaborine 
 was obtained in 70% yield ( entry 7 ) .
most importantly , cis-1-propenyltrifluoroborate was successfully employed in the reaction , 
 affording the product in high yield without isomerization of the alkene 
 ( entry 3 ) .
the scalable nature of the cross - coupling reaction was 
 demonstrated by performing the coupling on a 4.5 mmol scale ( 1 g of 
 azaborine ) with one - third palladium loading ( 2 mol % ) , which provided 
 the desired product in similar yield ( entry 8) .
reaction completed on a 4.5 mmol 
 scale with 2.0 mol % pd(dppf)cl2 . reaction conditions ( unless otherwise 
 noted ) : 1.0 equiv of 3-bromo-2-methyl-2,1-borazaronaphthalene , 1.1 
 equiv of potassium alkenyltrifluoroborate , 6.0 mol % pd(dppf)cl2 , 3.0 equiv of base , 1:1 toluene / h2o , and 60 c 
 for 18 h. the developed 
 reaction conditions were extended to cross - coupling 
 of 3-bromo-2-phenyl-2,1-borazaronaphthalene with an array of potassium 
 alkenyltrifluoroborates to demonstrate that azaborine can also be 
 substituted with an aryl group on the boron .
six different alkenyltrifluoroborates 
 were employed in the coupling and provided the desired product in 
 yields up to 90% .
the mild reaction conditions of the coupling were 
 demonstrated in the successful coupling of an alkenyltrifluoroborate 
 with an alkyl chloride substituent , affording the desired product 
 in 90% yield ( table 3 , entry 2 ) .
cyclic alkenyltrifluoroborates were successfully 
 engaged in the reaction as the desired products were obtained in high 
 yields ( entries 3 , 4 , and 6 ) .
reaction 
 conditions ( unless otherwise 
 noted ) : 1.0 equiv of 3-bromo-2-phenyl-2,1-borazaronaphthalene , 1.1 
 equiv of potassium alkenyltrifluoroborate , 6.0 mol % pd(dppf)cl2 , 3.0 equiv of base , 1:1 toluene / h2o , and 60 c 
 for 18 h. to demonstrate 
 the versatility of this method , an array of brominated 
 2,1-borazaronaphthalenes were synthesized and subjected to the developed 
 reaction conditions with 1-decenyltrifluoroborate as the nucleophile 
 in the reaction .
the cross - coupled products were obtained with secondary 
 cyclic and acyclic groups on boron in yields up to 90% ( table 4 , entries 1 
 and 2 ) .
azaborines with various substitution patterns on the arene 
 of boron were suitable electrophiles for coupling as the cross - coupled 
 products were isolated in high yield ( entries 35 ) .
substitution 
 on the nitrogen of the 2,1-borazaronaphthalenes did not affect the 
 coupling as reactions with both n - allyl and n - benzyl substituents provided the desired product in high 
 yields ( entries 6 and 7 ) .
reaction conditions 
 ( unless otherwise 
 noted ) : 1.0 equiv of 3-bromo-2,1-borazaronaphthalene , 1.1 equiv of 
 potassium alkenyltrifluoroborate , 6.0 mol % pd(dppf)cl2 , 3.0 equiv of base , 1:1 toluene / h2o , and 60 c for 
 18 h. to demonstrate that 
 the developed reaction conditions can be directly 
 applied to the functionalization of other azaborines , 6-bromo-2-methyl-3-phenyl-2,1-borazaronaphthalene 
 was subjected to the reaction ( eq 1 ) . the desired 
 product was obtained in 83% yield to afford c6-alkenyl - substituted 
 2,1-borazaronaphthalenes , examples of which are absent in the literature.1 the reaction conditions were then extended to cross - coupling 
 of 
 3,6-dibrominated 2,1-borazaronaphthalene .
the addition of 2.2 equiv 
 of 1-propenyltrifluoroborate provides a doubly cross - coupled product 
 in 76% yield ( eq 2).2 in conclusion , a general method for suzuki 
miyaura 
 cross - coupling 
 of brominated 2,1-borazaronaphthalenes with potassium alkenyltrifluoroborates 
 has been developed .
azaborines with alkyl and aryl groups on boron 
 and with or without substitution on nitrogen are suitable reagents 
 for the coupling . through this route ,
b nmr spectra 
 were obtained on a spectrometer equipped with the appropriate decoupling 
 accessories .
all b nmr chemical shifts were referenced 
 to external bf3oet2 ( 0.0 ppm ) with a negative 
 sign indicating an upfield shift .
data are presented as follows : chemical 
 shift ( ppm ) , multiplicity ( s = singlet , d = doublet , t = triplet , 
 q = quadruplet , m = multiplet , br = broad ) , coupling constant j ( hz ) , and integration .
analytical thin - layer chromatography 
 ( tlc ) was performed on tlc silica gel plates ( 0.25 mm ) precoated with 
 a fluorescent indicator .
hrms data were obtained 
 by either esi or ci using a tof mass spectrometer .
2,1-borazaronaphthalenes 
 were synthesized and brominated according to methods previously described in 
 the literature .
the title compound was obtained as a white solid in 90% yield ( 1.0 
 mmol scale , 316.7 mg ) : mp 98103 c ; h nmr 
 ( 500 mhz , cdcl3 )  8.49 ( s , 1h ) , 8.07 ( s , 1h ) , 7.98 
 ( d , j = 7.8 hz , 2h ) , 7.72 ( d , j = 
 7.8 hz , 2h ) , 7.64 ( d , j = 7.9 hz , 1h ) , 7.517.49 
 ( m , 1h ) , 7.34 ( d , j = 8.1 hz , 1h ) , 7.307.27 
 ( m , 1h ) ; c nmr ( 125.8 mhz , cdcl3 )  
 147.3 , 139.0 , 133.6 , 131.2 ( d , j = 32.5 hz ) , 129.7 , 
 129.2 , 126.5 ( q , j = 275.8 hz ) , 125.3 , 124.6 ( q , j = 3.6 hz ) , 122.5 , 118.4 ; b nmr ( 128.38 mhz , 
 cdcl3 )  32.9 ; ir ( neat ) 3367 , 2923 , 1556 , 1427 , 
 1120 , 1070 cm ; hrms ( ci ) m / z
[ m + h ] calcd for c15h11bnf3br 352.9825 , 
 found 352.9802 . to a biotage
10 ml microwave vial equipped with a magnetic stir 
 bar were added 3-bromo-2,1-alkenyltrifluoroborate ( 1.1 mmol , 1.1 equiv ) , 
 cs2co3 ( 3.0 mmol , 977 mg ) , pd(dppf)cl2 ( 6.0 mol % , 42 mg ) , and potassium alkenyltrifluoroborate ( 1.0 mmol , 
 1.0 equiv ) . the vial was sealed with a cap , lined with a teflon septum , 
 and evacuated and purged with argon gas three times .
anhydrous degassed 
 toluene ( 1.0 ml ) and deionized h2o ( 1.0 ml ) were added 
 under argon gas .
the reaction mixture was heated at 60 c for 
 18 h. after cooling to rt , the reaction mixture was extracted with 
 etoac ( 3  10 ml ) and dried ( mgso4 ) . after being concentrated 
 in vacuo , the product was isolated by flash column chromatography 
 and eluted with a gradient of etoac in hexanes ( 0 to 10% etoac ) .
the title compound was obtained as a yellow 
 solid in 88% yield ( 235.8 mg ) : mp 8993 c ; h nmr ( 500 mhz , cdcl3 )  7.79 ( s , 1h ) , 7.72 ( s , 
 1h ) , 7.58 ( d , j = 7.5 hz , 1h ) , 7.347.37 ( m , 
 1h ) , 7.18 ( d , j = 8.1 hz , 1h ) , 7.157.12 ( m , 
 1h ) , 5.245.23 ( m , 1h ) , 5.12 ( d , j = 2.5 hz , 
 1h ) , 3.67 ( t , j = 4.6 hz , 4h ) , 3.31 ( s , 2h ) , 2.48 
 ( br , 4h ) , 0.79 ( s , 3h ) ; c nmr ( 125.8 mhz , cdcl3 )  149.0 , 140.1 , 129.6 , 128.1 , 125.0 , 121.0 , 117.4 , 114.2 , 
 67.3 , 64.8 , 53.9 ; b nmr ( 128.38 mhz , cdcl3 )  36.7 ; ir ( neat ) 3319 , 2928 , 1566 , 1434 , 1109 , 891 cm ; hrms ( esi+ ) m / z [ m + h ] calcd for c16h22bn2o 269.1825 , found 269.1820 .
the title compound was obtained as a yellow 
 solid in 98% yield ( 179.3 mg ) : mp 6975 c;h nmr ( 500 mhz , cdcl3 )  7.76 ( s , 1h ) , 7.65 ( s , 
 1h ) , 7.56 ( d , j = 7.8 hz , 1h ) , 7.367.29 ( m , 
 1h ) , 7.16 ( d , j = 8.0 hz , 1h ) , 7.137.10 ( m , 
 1h ) , 6.59 ( d , j = 15.6 hz , 1h ) , 6.196.12 
 ( m , 1h ) , 1.91 ( dd , j = 6.6 , 1.5 hz , 3h ) , 0.85 ( s , 
 3h ) ; c nmr ( 125.8 mhz , cdcl3 )  139.5 , 
 138.7 , 134.8 , 129.3 , 127.6 , 126.5 , 125.6 , 121.0 , 117.4 , 19.4 ; b nmr ( 128.38 mhz , cdcl3 )  37.2 ; ir ( neat ) 
 3364 , 2924 , 1614 , 1457 , 1343 cm ; hrms ( ci ) m / z [ m ] calcd for c12h14bn 183.1219 , found 183.1216 .
the title compound was obtained as a brown 
 solid in 87% yield ( 159.2 mg ) : mp 98103 c ; h nmr ( 500 mhz , cdcl3 )  7.42 ( s , 1h ) , 7.68 ( s , 
 1h ) , 7.59 ( d , j = 7.8 hz , 1h ) , 7.377.34 ( m , 
 1h ) , 7.19 ( d , j = 8.0 hz , 1h ) , 7.187.13 ( m , 
 1h ) , 6.576.54 ( m , 1h ) , 5.725.79 ( m , 1h ) , 1.85 ( dd , j = 7.0 , 1.8 hz , 3h ) , 0.74 ( s , 3h ) ; c nmr ( 125.8 
 mhz , cdcl3 )  140.8 , 139.6 , 132.1 , 129.4 , 127.8 , 
 125.3 , 125.0 , 121.0 , 117.6 , 14.8 ; b nmr ( 128.38 mhz , 
 cdcl3 )  37.3 ; ir ( neat ) 3364 , 2925 , 1611 , 1560 , 
 1454 cm ; hrms ( ci ) m / z [ m ] calcd for c12h14bn 183.1219 , found 183.1213 .
the title compound was obtained as a yellow 
 oil in 69% 
 yield ( 126.2 mg ) .
h nmr ( 500 mhz , cdcl3 )  
 7.80 ( s , 1h ) , 7.68 ( s , 1h ) , 7.62 ( d , j = 7.7 hz , 
 1h ) , 7.397.36 ( m , 1h ) ,
7.197.15 ( m , 2h ) , 5.215.11 
 ( m , 1h ) , 5.07 ( d , j = 1.9 hz , 1h ) , 2.16 ( s , 3h ) , 
 0.87 ( s , 3h ) ; c nmr ( 125.8 mhz , cdcl3 )  
 148.4 , 139.6 , 139.2 , 129.6 , 128.0 , 125.1 , 121.0 , 117.4 , 113.0 , 23.9 ; b nmr ( 128.38 mhz , cdcl3 )  36.9 ; ir ( neat ) 
 3368 , 2933 , 1567 , 1462 , 1453 cm ; hrms ( ci ) m / z [ m ] calcd for c12h14bn 183.1219 , found 183.1220 .
the title compound was 
 obtained 
 as a yellow oil in 82% yield ( 184.5 mg ) .
h nmr ( 500 mhz , 
 cdcl3 )  7.75 ( s , 1h ) , 7.73 ( s , 1h ) , 7.59 ( d , j = 7.8 hz , 1h ) , 7.347.38 ( m , 1h ) , 7.18 ( d , j = 8.1 hz , 1h ) , 7.167.13 ( m , 1h ) , 5.835.82 
 ( m , 1h ) , 4.364.35 ( m , 2h ) , 3.97 ( t , j = 5.4 
 hz , 2h ) , 2.522.49 ( m , 2h ) , 0.84 ( s , 3h ) ; c nmr 
 ( 125.8 mhz , cdcl3 )  138.6 , 137.6 , 137.5 , 128.5 , 
 127.0 , 124.1 , 121.9 , 120.1 , 116.4 , 65.2 , 63.9 , 28.1 ; b nmr ( 128.38 mhz , cdcl3 )  36.7 ; ir ( neat ) 3325 , 
 2923 , 1572 , 1458 , 1032 cm ; hrms ( ci ) m / z [ m ] calcd for c14h16bno 225.1325 , found 225.1336 .
the title compound was obtained as a white 
 solid in 81% yield ( 227.6 mg ) : mp 8388 c ; h nmr ( 500 mhz , cdcl3 )  7.73 ( s , 1h ) , 7.69 ( s , 
 1h ) , 7.547.56 ( m , 1h ) , 7.327.35 ( m , 1h ) , 7.16 ( d , j = 8 hz , 1h ) , 7.137.10 ( m , 1h ) , 5.665.65 
 ( m , 1h ) , 4.054.02 ( m , 4h ) , 2.632.59 ( m , 2h ) , 2.502.49 
 ( m , 2h ) , 1.93 ( t , j = 6.5 hz , 2h ) , 0.81 ( s , 3h ) ; c nmr ( 125.8 mhz , cdcl3 )  140.9 , 139.5 , 
 138.7 , 129.4 , 127.8 , 125.2 , 121.1 , 120.9 , 117.3 , 108.3 , 64.7 , 36.5 , 
 31.8 , 28.7 ; b nmr ( 128.38 mhz , cdcl3 )  
 37.0 ; ir ( neat ) 3308 , 2927 , 1609 , 1460 , 1047 cm ; hrms ( ci ) m / z [ m ] calcd for c17h20bno2 281.1587 , 
 found 281.1593 .
the title compound was obtained as a light 
 yellow solid in 70% 
 yield ( 118.3 mg ) : mp 5256 c ; h nmr ( 500 
 mhz , cdcl3 )  7.70 ( s , 1h ) , 7.64 ( s , 1h ) , 7.55 ( d , j = 7.8 hz , 1h ) , 7.337.30 ( m , 1h ) , 7.15 ( d , j = 8.0 hz , 1h ) , 7.107.08 ( m , 1h ) , 6.736.66 
 ( m , 1h ) , 5.875.85 ( m , 1h ) , 5.745.71 , ( m , 1h ) , 0.70 
 ( s , 3h ) ; c nmr ( 125.8 mhz , cdcl3 )  
 140.7 , 140.3 , 139.9 , 129.6 , 128.2 , 125.3 , 121.2 , 117.5 , 114.8 ; b nmr ( 128.38 mhz , cdcl3 )  37.2 ; ir ( neat ) 
 3365 , 2927 , 1610 , 1457 cm ; hrms ( ci )
the title compound was obtained as a white 
 solid in 90% yield ( 233.1 mg ) : mp 7276 c ; h nmr ( 500 mhz , cdcl3 )  7.73 ( s , 1h ) , 7.69 ( s , 
 1h ) , 7.60 ( d , j = 8.0 hz , 1h ) , 7.417.37 ( m , 
 1h ) , 7.207.15 ( m , 2h ) , 5.595.56 ( m , 1h ) ,
2.782.72 
 ( m , 2h ) , 2.672.64 ( m , 2h ) , 2.252.17 ( m , 2h ) , 0.82 
 ( s , 3h ) ; c nmr ( 125.8 mhz , cdcl3 )  
 140.8 , 139.5 , 139.1 , 129.4 , 128.0 , 124.9 , 123.3 ( t , j = 239.6 hz ) , 121.0 , 118.2 ( t , j = 4.9 hz ) , 117.3 , 
 35.3 ( t , j = 26.4 hz ) , 31.0 ( t , j = 24.4 hz ) , 27.8 ( t , j = 5.2 hz ) ; b nmr ( 128.38 mhz , cdcl3 )  36.2 ; ir ( neat ) 3397 , 
 2936 , 1613 , 1560 , 1425 , 1058 , cm ; hrms ( ci )
the title compound was obtained as a yellow 
 solid in 75% yield ( 210.7 mg ) : mp 5862 c ; h nmr ( 500 mhz , cdcl3 )  7.79 ( s , 1h ) , 7.65 ( s , 
 1h ) , 7.57 ( d , j = 7.75 hz , 1h ) , 7.347.31 
 ( m , 1h ) , 7.167.11 ( m , 2h ) , 6.58 ( d , j = 15.5 
 hz , 1h ) , 6.186.12 ( m , 1h ) , 2.262.22 ( m , 2h ) , 1.531.47 
 ( m , 2h ) , 1.401.28 ( m , 10h ) , 0.92 ( t , j = 
 6.9 hz , 3h ) , 0.86 ( s , 3h ) ; c nmr ( 125.8 mhz , cdcl3 )  139.5 , 138.8 , 133.4 , 132.2 , 129.3 , 127.6 , 125.6 , 
 121.0 , 117.4 , 34.0 , 32.2 , 30.0 , 29.9 , 29.7 , 29.6 , 23.0 , 14.4 ; b nmr ( 128.38 mhz , cdcl3 )  37.1 ; ir ( neat ) 
 3366 , 2921 , 1556 , 1463 , 977 cm ; hrms ( ci ) m / z [ m ] calcd for c19h28bn 281.2315 , found 281.2328 .
the title compound 
 was obtained as a white solid in 65% yield ( 210.6 mg ) : mp 8387 
 c ; h nmr ( 500 mhz , cdcl3 )  7.75 
 ( s , 1h ) , 7.69 ( s , 1h ) , 7.57 ( d , j = 7.7 hz , 1h ) , 
 7.367.33 ( m , 1h ) , 7.17 ( d , j = 8.0 hz , 1h ) , 
 7.147.11 ( m , 1h ) , 5.71 ( br , 1h ) , 4.07 ( br , 2h ) , 3.64 ( t , j = 5.5 hz , 2h ) , 4.47 ( br , 2h ) , 1.52 ( s , 9h ) , 0.80 ( s , 3h ) ; c nmr ( 125.8 mhz , cdcl3 )  155.3 , 139.9 , 
 139.6 , 138.7 , 129.5 , 128.0 , 125.1 , 121.1 , 120.7 , 117.4 , 79.7 , 44.3 , 
 40.1 , 34.9 , 29.4 , 28.8 ; b nmr ( 128.38 mhz , cdcl3 )  32.0 ; ir ( neat ) 3327 , 2975 , 1677 , 1563 , 1423 , 1163 cm ; hrms ( ci ) m / z [ m 
 + h ] calcd for c19h26bn2o2 325.2087 , found 325.2080 .
the title compound was obtained as a yellow 
 solid in 83% yield ( 226.5 mg ) : mp 7477 c ; h nmr ( 500 mhz , cdcl3 )  7.66 ( s , 1h ) , 7.59 ( s , 
 1h ) , 7.55 ( d , j = 7.7 hz , 1h ) , 7.387.36 ( m , 
 1h ) , 7.357.31 ( m , 2h ) , 7.227.13 ( m , 5h ) , 6.58 ( dd , j = 11.5 , 1.4 hz , 1h ) , 5.69 ( dt , j = 11.5 , 
 7.2 hz , 1h ) , 2.79 ( t , j = 7.7 hz , 2h ) , 2.702.45 
 ( m , 2h ) , 0.73 ( s , 3h ) ; c nmr ( 125.8 mhz , cdcl3 )  142.3 , 140.6 , 139.7 , 132.1 , 129.9 , 129.5 , 128.9 , 128.6 , 
 127.9 , 126.1 , 125.3 , 121.0 , 117.5 , 36.7 , 30.6 ; b nmr 
 ( 128.38 mhz , cdcl3 )  37.4 ; ir ( neat ) 3373 , 2925 , 
 1556 , 1452 , 746 , 703 cm ; hrms ( ci ) m / z [ m ] calcd for c19h20bn 273.1689 , found 273.1683 .
the title compound was obtained as a white 
 oil in 73% yield ( 250.3 mg ) .
h nmr ( 500 mhz , cdcl3 )  8.05 ( s , 1h ) , 7.91 ( s , 1h ) , 7.777.75 ( m , 
 2h ) , 7.69 ( d , j = 8.0 hz , 1h ) , 7.517.47 ( m , 
 3h ) , 7.427.39 ( s , 1h ) , 7.26 ( d , j = 8.0 hz , 
 1h ) , 7.22 ( t , j = 7.5 hz , 1h ) , 6.70 ( d , j = 15.5 hz , 1h ) , 6.07 ( dt , j = 15.4 , 7.0 hz , 1h ) , 
 2.21 ( q , j = 7.0 hz , 2h ) , 1.501.45 ( m , 2h ) , 
 1.401.35 ( m , 10h ) , 0.96 ( t , j = 7.0 hz , 3h ) ; c nmr ( 125.8 mhz , cdcl3 )  139.8 , 139.6 , 
 133.2 , 132.7 , 132.3 , 129.5 , 128.8 , 128.2 , 128.0 , 125.9 , 121.0 , 118.0 , 
 33.7 , 32.2 , 29.9 , 29.8 , 29.7 , 29.6 , 23.0 , 14.4 ; b nmr 
 ( 128.38 mhz , cdcl3 )  34.4 ; ir ( neat ) 3370 , 2923 , 
 2852 , 1421 , 749 cm ; hrms ( ci ) m / z [ m + na ] calcd for c24h30bnna 366.2369 , found 366.2375 .
the title compound was obtained as a brown 
 oil 
 in 90% yield ( 288.9 mg ) .
h nmr ( 500 mhz , cdcl3 )  8.03 ( s , 1h ) , 7.92 ( s , 1h ) , 7.72 ( dd , j = 7.25 , 1.5 hz , 2h ) , 7.68 ( d , j = 7.5 hz , 1h ) , 
 7.507.46 ( m , 3h ) , 7.427.39 ( m , 1h ) , 7.26 ( d , j = 8 hz , 1h ) , 7.237.20 ( m , 1h ) , 6.68 ( d , j = 15.5 hz , 1h ) , 6.00 ( dt , j = 15.4 , 7.0 
 hz , 1h ) , 3.57 ( t , j = 6.5 hz , 2h ) , 2.232.19 
 ( m , 2h ) , 1.861.83 ( m , 2h ) , 1.621.58 ( m , 2h ) ; c nmr ( 125.8 mhz , cdcl3 )  140.1 , 139.6 , 
 133.4 , 133.1 , 131.1 , 129.5 , 128.8 , 128.2 , 128.1 , 125.7 , 121.7 , 118.0 , 
 45.3 , 32.7 , 32.3 , 27.0 ; b nmr ( 128.38 mhz , cdcl3 )  35.0 ; ir ( neat ) 3373 , 2933 , 1558 , 1421 , 969 , 752 cm ; hrms ( ci ) m / z [ m ] calcd for c20h21bncl 321.1456 , found 
 321.1463 . the title compound was obtained as a yellow 
 solid 
 in 79% yield ( 225.1 mg ) : mp 8892 c ; h nmr 
 ( 500 mhz , cdcl3 )  7.95 ( s , 1h ) , 7.85 ( s , 1h ) , 7.797.7.78 
 ( m , 2h ) , 7.66 ( d , j = 7.5 hz , 1h ) , 7.457.39 
 ( m , 4h ) , 7.28 ( d , j = 8.0 hz , 1h ) , 7.227.19 
 ( m , 1h ) , 5.735.71 ( m , 1h ) ,
2.192.13 ( m , 4h ) , 1.661.65 
 ( m , 4h ) ; c nmr ( 125.8 mhz , cdcl3 )  
 142.3 , 140.5 , 139.6 , 132.8 , 129.5 , 128.9 , 128.1 , 128.0 , 125.6 , 124.2 , 
 121.5 , 117.9 , 29.9 , 26.1 , 23.5 , 22.6 ; b nmr ( 128.38 mhz , 
 cdcl3 )  34.0 ; ir ( neat ) 3375 , 2920 , 1558 , 1451 , 
 751 cm ; hrms ( ci ) m / z [ m ] calcd for c20h20bn 285.1689 , 
 found 285.1705 .
the title compound was 
 obtained 
 as a white solid in 86% yield ( 246.8 mg ) : mp 112115 c ; h nmr ( 500 mhz , cdcl3 )  8.02 ( s , 1h ) , 7.91 
 ( s , 1h ) , 7.767.68 ( m , 2h ) , 7.69 ( d , j = 7.5 
 hz , 1h ) , 7.477.42 ( m , 4h ) , 7.29 ( d , j = 8.1 
 hz , 1h ) , 7.247.21 ( m , 1h ) , 5.755.73 ( m , 1h ) , 4.314.29 
 ( m , 2h ) , 3.84 ( t , j = 5.5 hz , 2h ) , 2.30 ( td , j = 5.3 , 2.7 hz , 2h ) ; c nmr ( 125.8 mhz , cdcl3 )  140.9 , 139.7 , 139.4 , 132.7 , 129.6 , 128.9 , 128.4 , 
 128.2 , 125.3 , 122.8 , 121.7 , 118.0 , 66.2 , 64.9 , 29.5 ; b nmr ( 128.38 mhz , cdcl3 )  34.0 ; ir ( neat ) 3287 , 
 2930 , 1564 , 1455 ,
1229 , 758 cm ; hrms ( ci ) m / z [ m ] calcd for c19h18bno 287.1481 , found 287.1487 .
the title compound was obtained as a brown 
 oil in 76% 
 yield ( 186.2 mg ) .
h nmr ( 500 mhz , cdcl3 )  
 7.96 ( br , 2h ) , 7.927.81 ( m , 2h ) , 7.70 ( d , j = 7.5 hz , 1h ) , 7.477.43 ( m , 4h ) , 7.29 ( d , j = 8.0 hz , 1h ) , 7.257.22 ( m , 1h ) , 5.065.02 ( m , 2h ) , 
 1.99 ( s , 3h ) ; c nmr ( 125.8 mhz , cdcl3 )  
 149.2 , 140.9 , 139.5 , 132.6 , 129.5 , 128.7 , 128.2 , 128.0 , 125.2 , 121.5 , 
 117.8 , 113.0 , 24.1 ; b nmr ( 128.38 mhz , cdcl3 )  33.6 ; ir ( neat ) 3367 , 2925 , 1573 , 1463 , 757 cm ; hrms ( ci ) m / z [ m ] calcd for c17h16bn 245.1376 , found 245.1377 .
the title compound was obtained as a white 
 solid in 81% yield ( 277.8 mg ) : mp 108112 c ; h nmr ( 500 mhz , cdcl3 )  7.98 ( s , 1h ) , 7.90 ( s , 
 1h ) , 7.807.78 ( m , 2h ) , 7.65 ( d , j = 7.5 hz , 
 1h ) , 7.457.39 ( m , 4h ) , 7.28 ( d , j = 8.0 hz , 
 1h ) , 7.217.18 ( m , 1h ) , 6.625.60 ( m , 1h ) , 4.053.98 
 ( m , 4h ) , 2.472.46 ( m , 2h ) , 2.38 ( td , j = 
 6.3 , 1.6 hz , 2h ) , 1.79 ( t , j = 6.5 hz , 2h ) ; c nmr ( 125.8 mhz , cdcl3 )  141.9 , 141.1 , 
 139.6 , 132.7 ,
129.4 , 128.9 , 128.1 , 128.1 , 125.3 , 121.5 , 121.1 , 117.8 , 
 108.2 , 64.5 , 36.4 , 31.6 , 29.0 ; b nmr ( 128.38 mhz , cdcl3 )  34.4 ; ir ( neat ) 3326 , 1560 , 1421 , 1112 , 755 cm ; hrms ( ci ) m / z [ m ] calcd for c22h22bno2 343.1744 , 
 found 343.1756 .
the title compound was obtained as a colorless 
 oil in 81% yield ( 247.8 mg ) .
h nmr ( 500 mhz , cdcl3 )  7.92 ( s , 1h ) , 7.67 ( s , 1h ) , 7.62 ( d , j = 7.8 hz , 1h ) , 7.397.35 ( m , 1h ) , 7.24 ( d , j = 8.0 hz , 1h ) , 7.187.15 ( m , 1h ) , 6.69 ( dd , j = 15.6 , 0.4 hz , 1h ) , 6.136.18 ( m , 1h ) , 2.312.26 
 ( m , 2h ) , 1.961.92 ( m , 1h ) , 1.571.54 ( m , 2h ) , 1.431.35 
 ( m , 10h ) , 1.23 ( d , j = 7.3 hz , 6h ) , 0.97 ( t , j = 6.9 hz , 3h ) ; c nmr ( 125.8 mhz , cdcl3 )  139.6 , 138.4 , 132.2 , 131.1 , 129.3 , 127.6 , 125.7 , 
 121.2 , 117.7 , 33.8 , 32.2 , 30.0 , 29.9 , 29.7 , 29.6 , 23.0 , 19.6 , 14.4 ; b nmr ( 128.38 mhz , cdcl3 )  38.8 ; ir ( neat ) 
 3424 , 2924 , 1560 , 1427 , 969 cm ; hrms ( ci ) m / z [ m ] calcd for c21h32bn 309.2628 , found 309.2633 .
the title compound was obtained as a yellow 
 solid in 90% yield ( 276.3 mg ) : mp 5155 c ; h nmr ( 500 mhz , cdcl3 )  7.92 ( s , 1h ) , 7.56 ( d , j = 7.7 hz , 1h ) , 7.327.29 ( m , 1h ) , 7.18 ( s , 1h ) , 
 7.11 ( t , j = 7.9 hz , 2h ) , 6.69 ( d , j = 15.6 hz , 1h ) , 6.386.24 ( m , 1h ) , 2.25 ( q , j = 7.2 hz , 2h ) , 1.521.48 ( m , 2h ) , 1.391.28 ( m , 10h ) , 
 0.920.89 ( m , 5h ) , 0.660.55 ( m , 3h ) ;
c 
 nmr ( 125.8 mhz , cdcl3 )  139.5 , 138.5 , 132.8 , 132.4 , 
 129.3 , 127.6 , 125.5 , 121.0 , 117.4 , 34.0 , 32.2 , 30.0 , 29.9 , 29.7 , 29.6 , 
 23.0 , 14.4 , 6.0 ; b nmr ( 128.38 mhz , cdcl3 ) 
  37.1 ; ir ( neat ) 3374 , 3010 , 2920 , 1557 , 1428 , 1105 cm ; hrms ( ci ) m / z [ m ] calcd for c21h30bn 307.2471 , found 
 307.2484 .
the title compound was obtained as a yellow 
 oil in 88% yield ( 317.6 mg ) .
h nmr ( 500 mhz , cdcl3 )  8.01 ( s , 1h ) , 7.85 ( s , 1h ) , 7.717.65 ( m , 
 3h ) , 7.417.37 ( m , 1h ) , 7.25 ( d , j = 8.5 hz , 
 1h ) , 7.227.19 ( m , 1h ) , 7.177.14 ( m , 2h ) , 6.62 ( dd , j = 15.6 , 0.7 hz , 1h ) , 6.01 ( dt , j = 15.5 , 
 7.0 hz , 1h ) , 2.17 ( qd , j = 7.3 , 1.3 hz , 2h ) , 1.481.49 
 ( m , 2h ) , 1.361.29 ( m , 10h ) , 0.92 ( t , j = 
 7.0 hz , 3h ) ; c nmr ( 125.8 mhz , cdcl3 )  
 163.6 ( d , j = 252 hz ) , 139.8 , 139.3 , 134.9 ( d , j = 7.4 hz ) , 132.4 , 132.3 , 129.3 , 127.9 , 125.7 , 121.6 , 117.8 , 
 115.1 ( d , j = 19.6 hz ) , 33.5 , 32.0 , 29.7 , 29.6 , 29.5 , 
 29.4 , 22.8 , 14.2 ; b nmr ( 128.38 mhz , cdcl3 )  33.9 ; ir ( neat ) 3375 , 2923 , 1595 , 1224 , 832 cm ; hrms ( ci ) m / z [ m ] calcd for c24h29bnf 361.2377 , found 361.2368 . the title compound was obtained as a colorless 
 oil in 81% yield ( 302.1 mg ) .
h nmr ( 500 mhz , cdcl3 )  8.04 ( s , 1h ) , 7.94 ( s , 1h ) , 7.68 ( d , j = 7.7 hz , 1h ) , 7.437.40 ( m , 2h ) , 7.32 ( d , j = 7.2 hz , 1h ) , 7.297.27 ( m , 2h ) , 7.22 ( t , j = 7.5 hz , 1h ) , 7.01 ( dd , j = 8.2 , 2.7 hz , 1h ) , 
 6.68 ( d , j = 15.6 hz , 1h ) , 6.106.04 ( m , 1h ) , 
 3.89 ( s , 3h ) , 2.212.16 ( m , 2h ) , 1.471.43 ( m , 2h ) , 
 1.361.28
( m , 10h ) , 0.93 ( t , j = 6.9 hz , 3h ) ; c nmr ( 125.8 mhz , cdcl3 )  159.4 , 139.8 , 
 139.5 , 132.5 , 132.3 , 129.5 , 129.4 , 128.0 , 125.9 , 125.5 , 121.7 , 118.3 , 
 118.0 , 114.4 , 55.4 , 33.7 , 32.2 , 29.9 , 29.8 , 29.6 , 29.6 , 23.0 , 14.4 ; b nmr ( 128.38 mhz , cdcl3 )  34.8 ; ir ( neat ) 
 3366 , 2924 , 1558 , 1451 , 1236 , 971 , 761 cm ; hrms 
 ( ci ) m / z [ m + h ] calcd 
 for c25h33bno 374.2655 , found 374.2661 .
the title compound was obtained as a light 
 brown oil in 83% yield ( 341.3 mg ) .
h nmr ( 500 mhz , cdcl3 )  8.03 ( s , 1h ) , 7.91 ( s , 1h ) , 7.80 ( d , j = 7.7 hz , 2h ) , 7.707.68 ( m , 3h ) , 7.427.39 ( m , 1h ) , 
 7.27 ( d , j = 8.1 hz , 1h ) , 7.227.21 ( m , 1h ) , 
 6.56 ( dd , j = 15.6 , 1.0 hz , 1h ) , 5.605.94 
 ( m , 1h ) , 2.14 ( m , 2h ) , 1.421.39 ( m , 2h ) , 1.271.32 
 ( m , 10h ) , 0.90 ( t , j = 5.1 hz , 3h ) ; c nmr ( 125.8 mhz , cdcl3 )  140.1 , 139.1 , 133.1 , 
 132.8 , 131.9 , 130.4 ( d , j = 32.3 hz ) , 129.4 , 128.1 , 
 126.3 ( q , j = 272.2 hz ) , 125.8 , 124.6 ( q , j = 3.7 hz ) , 121.9 , 117.9 , 33.5 , 32.0 , 29.6 , 29.5 , 29.3 , 
 22.8 , 14.2 ; b nmr ( 128.38 mhz , cdcl3 )  
 34.5 ; ir ( neat ) 3395 , 2924 , 1559 , 1323 , 969 , 836 cm ; hrms ( ci ) m / z [ m ] calcd for c25h29bnf3 411.2345 , 
 found 411.2353 .
the title compound was obtained as a light 
 yellow oil in 62% yield ( 199.0 mg ) .
h nmr ( 500 mhz , cdcl3 )  7.84 ( s , 1h ) , 7.61 ( d , j = 7.0 
 hz , 1h ) , 7.39 ( dd , j = 4.7 , 1.2 hz , 2h ) , 7.177.13 
 ( m , 1h ) , 6.66 ( dd , j = 15.5 , 1.0 hz , 1h ) , 6.106.01 
 ( m , 2h ) , 5.15 ( dd , j = 10.5 , 1.4 hz , 1h ) , 4.99 ( dd , j = 17.2 , 1.3 hz , 1h ) , 4.72 ( dd , j = 4.1 , 
 2.0 hz , 2h ) , 2.272.22 ( m , 2h ) , 1.541.49 ( m , 2h ) , 1.411.27 
 ( m , 10h ) , 0.930.89 ( m , 6h ) ; c nmr ( 125.8 mhz , 
 cdcl3 )  141.2 , 137.7 , 134.7 , 132.7 , 131.3 , 130.2 , 
 127.8 , 126.7 , 120.8 , 115.9 , 115.5 , 49.8 , 33.8 , 32.2 , 30.1 , 29.9 , 29.7 , 
 29.6 , 23.0 , 14.4 ; b nmr ( 128.38 mhz , cdcl3 )  38.7 ; ir ( neat ) 2923 , 1556 , 1405 , 1212 , 968 cm ; hrms ( ci ) m / z [ m ] calcd for c22h32bn 321.2628 , found 321.2633 . the title compound was obtained as a light 
 brown oil in 90% yield ( 333.9 mg ) .
h nmr ( 500 mhz , cdcl3 )  7.97 ( s , 1h ) , 7.68 ( d , j = 7.0 
 hz , 1h ) , 7.357.27 ( m , 5h ) , 7.197.16 ( m , 3h ) , 6.78 
 ( dd , j = 15.6 , 0.6 hz , 1h ) , 6.19 ( dt , j = 15.5 , 6.9 hz , 1h ) , 5.38 ( s , 2h ) , 2.362.37 ( m , 2h ) , 1.631.57 
 ( m , 2h ) , 1.501.39 ( m , 10h ) , 1.000.98 ( m , 6h ) ; c nmr ( 125.8 mhz , cdcl3 )  141.3 , 138.8 , 
 138.02 , 132.7 , 131.4 , 130.2 , 129.0 , 127.9 , 127.1 , 126.9 , 126.1 , 120.9 , 
 115.9 , 51.4 , 33.8 , 32.2 , 30.1 , 29.9 , 29.8 , 29.7 , 23.0 , 14.4 ; b nmr ( 128.38 mhz , cdcl3 )  39.0 ; ir ( neat ) 
 2924 , 2853 , 1610 , 1492 , 1402 , 1360 , 967 cm ; hrms 
 ( ci ) m / z [ m ] calcd for 
 c26h34bn 371.2784 , found 371.2791 .
the title compound was obtained as a light 
 yellow oil in 80% yield ( 285.6 mg ) .
h nmr ( 500 mhz , cdcl3 )  8.04 ( s , 1h ) , 7.91 ( s , 1h ) , 7.68 ( d , j = 7.5 hz , 1h ) , 7.577.52 ( m , 2h ) , 7.427.37 ( m , 2h ) , 
 7.297.25 ( m , 2h ) , 7.21 ( t , j = 7.5 hz , 1h ) , 
 6.68 ( d , j = 15.5 hz , 1h ) , 6.07 ( dt , j = 15.4 , 7.0 hz , 1h ) , 2.47 ( s , 3h ) , 2.20 ( q , j = 
 6.9 hz , 2h ) , 1.491.46 ( m , 2h ) ,
1.391.33 ( m , 10h ) , 
 0.94 ( t , j = 6.9 hz , 3h ) ; c nmr ( 125.8 
 mhz , cdcl3 )  139.7 , 137.5 , 133.9 , 132.7 , 132.2 , 
 130.3 , 129.5 , 128.1 , 128.0 , 125.9 , 121.6 , 117.9 , 33.7 , 32.2 , 30.0 , 
 29.9 , 29.7 , 29.6 , 23.0 , 21.9 , 14.4 ; b nmr ( 128.38 mhz , 
 cdcl3 )  34.7 ; ir ( neat ) 3369 , 2923 , 2852 , 1612 , 
 1557 , 1450 , 969 cm ; hrms ( ci ) m / z [ m ] calcd for c25h32bn 357.2628 , found 357.2632 .
the title compound was obtained as a brown 
 oil in 83% yield ( 296.3 mg ) .
h nmr ( 500 mhz , cdcl3 )  7.85 ( s , 1h ) , 7.77 ( s , 1h ) , 7.57 ( d , j = 1.5 hz , 1h ) , 7.477.41 ( m , 5h ) , 7.337.31 ( m , 1h ) , 
 7.16 ( d , j = 8.5 hz , 1h ) , 6.46 ( d , j = 16.0 hz , 1h ) , 6.23 ( dt , j = 15.7 , 6.9 hz , 1h ) , 
 2.272.22 ( m , 2h ) ,
1.521.48 ( m , 2h ) , 1.391.28 
 ( m , 10h ) , 0.92 ( t , j = 7.0 hz , 3h ) , 0.83 ( s , 3h ) ; c nmr ( 125.8 mhz , cdcl3 )  145.1 , 141.8 , 
 139.0 , 131.3 , 130.0 , 129.6 , 128.5 , 128.4 , 127.2 , 126.3 , 126.0 , 125.3 , 
 117.7 , 33.4 , 32.2 , 29.8 , 29.8 , 29.6 , 29.6 , 23.0 , 14.4 ; b nmr ( 128.38 mhz , cdcl3 )  36.4 ; ir ( neat ) 3372 , 
 2924 , 2853 , 1617 , 1577 , 1456 , 962 , 762 cm ; hrms 
 ( ci ) m / z [ m ] calcd for 
 c25h32bn 357.2628 , found 357.2621 .
the title compound was obtained as a yellow 
 solid in 76% yield ( 169.4 mg ) : mp 106110 c ; h nmr ( 500 mhz , cdcl3 )  7.75 ( s , 1h ) , 7.60 ( s , 
 1h ) , 7.48 ( d , j = 1.5 hz , 1h ) , 7.38 ( dd , j = 8.3 , 1.9 hz , 1h ) , 7.07 ( d , j = 8.4 
 hz , 1h ) , 6.62 ( dd , j = 15.7 , 0.7 hz , 1h ) , 6.48 ( dd , j = 15.7 , 1.5 hz , 1h ) , 6.266.14 ( m , 2h ) , 1.951.93 
 ( m , 6h ) , 0.86 ( s , 3h ) ; c nmr ( 125.8 mhz , cdcl3 )  137.4 , 137.6 , 133.9 , 130.1 , 130.0 , 125.7 , 125.4 , 124.5 , 
 124.3 , 123.1 , 116.6 , 18.3 , 17.8 ; b nmr ( 128.38 mhz , cdcl3 )  37.2 ; ir ( neat ) 3371 , 2957 , 2910 , 1610 , 1557 , 1436 
 cm ; hrms ( ci ) m / z [ m ] calcd for c15h18bn 223.1532 , 
 found 223.1532 .
 conditions 
 have been developed for the palladium - catalyzed cross - coupling 
 of 3-bromo-2,1-borazaronaphthalenes with potassium alkenyltrifluoroborates . 
 
 twenty - seven alkenyl - substituted azaborines have been synthesized through 
 this method , providing access to a family of 2,1-borazaronaphthalenes 
 with alkenyl substitution at the c3 position . 
Introduction
Results and Discussion
Experimental Section