The Journal of Organic Chemistry
Article
7.13 (m, 2H), 6.23 (s, 1H), 5.10 (d, J = 6.0 Hz, 1H), 4.50 (d, J = 6.0
Hz, 1H), 1.47 (s, 9H), 1.45−1.42 (m, 6H), 1.28−1.21 (m, 6H), 0.94−
0.82 (m, 15H) ppm; 13C NMR (125 MHz, CDCl3): δ = 161.5, 156.0,
154.4, 129.3, 122.5, 122.4, 119.8, 110.4, 98.2, 79.6, 39.2, 28.8, 28.4,
27.4, 13.6, 11.1 ppm; HRMS (ESI): m/z calcd for C26H44O3NSn [M +
H]+: 538.2343. Found: 538.2331.
N-tert-Butyl 1-(Tributylstannyl)-3,4-dihydroisoquinoline-
2(1H)-carboxylate (1o). Colorless oil; IR (neat): 2956, 2871,
1690, 1603, 1456, 1364, 1294, 1234, 1173, 1039 cm−1; 1H NMR (500
MHz, CDCl3): δ = 7.09−6.86 (m, 3H), 6.85 (6.81 for rotamer) (d, J =
7.5 Hz, 1H), 5.32 (5.27) (s, 1H), 4.29−4.26 (3.85−3.30) (m, 1H),
3.35−3.30 (2.93−2.89) (m, 1H), 3.01−2.94 (2.73−2.66) (m, 2H),
1.50 (1.48) (s, 9H), 1.40−1.34 (m, 6H), 1.28−1.19 (m, 6H), 0.86−
0.76 (m, 15H) ppm; 13C NMR (125 MHz, CDCl3): δ = 153.7 (153.4),
139.9 (139.5), 131.5 (131.4), 128.9 (128.1), 126.3 (126.2), 123.94
(123.87), 123.7 (123.6), 79.8 (79.1), 49.8 (49.5), 41.9. 40.8, 28.90
(28.85), 28.6 (28.5), 27.44 (27.38), 13.59 (13.57), 10.5 (10.3) ppm.
HRMS (ESI): m/z calcd for C22H36O2NSn [M − Bu]+: 466.1768.
Found: 466.1766.
N-tert-Butyl 1-(Tributylstannyl)isoindoline-2-carboxylate
(1p). Colorless oil; IR (neat): 2956, 2853, 1688, 1463, 1365, 1257,
1220, 1119, 1023, 879 cm−1; 1H NMR (500 MHz, CDCl3): δ = 7.20−
7.06 (m, 3H), 7.00 (6.95 for rotamer) (d, J = 7.3 Hz, 1H), 5.10 (5.02)
(s, 1H), 4.97 (4.81) (d, J = 14.9 Hz, 1H), 4.54 (4.47) (d, J = 14.9 Hz,
1H), 1.52 (1.50) (s, 9H), 1.43−1.36 (m, 6H), 1.28−1.20 (m, 6H),
0.90−0.83 (m, 15H) ppm; 13C NMR (125 MHz, CDCl3): δ = 153.5
(153.2), 143.4 (143.1), 134.9 (134.4), 127.1 (127.0), 124.9 (124.8),
122.5 (122.3), 120.9 (120.1), 79.8 (79.0), 55.2 (55.1), 52.4 (52.1),
28.90 (28.86), 28.63 (28.56), 27.44 (27.38), 13.7 (13.6), 10.3 (10.1)
ppm. HRMS (ESI): m/z calcd for C21H34O2NSn [M − Bu]+:
452.1606. Found: 452.1602.
N-(1-Tributylstannyl-1-methylbenzyl)-tert-butanesulfona-
mide (1q). Pale yellow oil; IR (neat): 3267, 2955, 1597, 1493, 1375,
1293, 1129, 1080, 1023, 939 cm−1; 1H NMR (500 MHz, CDCl3): δ =
7.31 (d, J = 4.0 Hz, 4H), 7.13−7.11 (m, 1H), 3.99 (s, 1H), 1.92 (s,
3H), 1.44 (s, 9H), 1.38−1.19 (m, 12H), 0.90−0.77 (m, 15H) ppm;
13C NMR (125 MHz, CDCl3): δ = 148.5, 128.4, 125.0, 124.4, 59.7,
2-Methoxyphenyl(tributylstannyl)methyl Acetate (6g). Col-
orless oil; IR (neat): 2955, 2928, 2870, 2853, 1726, 1599, 1585, 1490,
1
1370, 1332 cm−1; H NMR (500 MHz, CDCl3): δ = 7.27 (d, J = 7.1
Hz, 1H), 7.10 (t, J = 7.5 Hz, 1H), 6.95 (t, J = 7.1 Hz, 1H), 6.79 (d, J =
7.5 Hz, 1H), 6.06 (s, 1H), 3.80 (s, 3H), 2.17 (s, 3H), 1.47−1.31 (m,
6H), 1.29−1.21 (m, 6H), 0.87−0.72 (m, 15H) ppm; 13C NMR (125
MHz, CDCl3): δ = 170.5, 153.0, 131.0, 125.4, 125.3, 120.6, 109.0,
69.4, 54.7, 28.7, 27.3, 20.9, 13.6, 10.1 ppm. HRMS (EI): m/z calcd for
C18H29O3Sn [M − Bu+]: 413.1139. Found: 413.1126.
1-Naphthyl(tributylstannyl)methyl Acetate (6h). Colorless oil;
IR (neat): 3058, 2955, 2926, 2871, 2852, 1721, 1593, 1509, 1463,
1
1397 cm−1; H NMR (500 MHz, CDCl3): δ = 7.86−7.84 (m, 2H),
7.66−7.62 (m, 1H), 7.49−7.43 (m, 4H), 7.00 (s, 1H), 2.14 (s, 3H),
1.34−1.26 (m, 6H), 1.19−1.12 (m, 6H), 0.83−0.70 (m, 15H) ppm;
13C NMR (125 MHz, CDCl3): δ = 170.7, 138.3, 133.6, 129.0, 128.5,
125.6, 125.58, 125.55, 125.50, 122.8, 120.6, 71.9, 28.6, 27.3, 21.1, 13.5,
10.6 ppm. HRMS (EI): m/z calcd for C21H29O2Sn [M − Bu+]:
433.1190. Found: 433.1180.
2-Naphthyl(tributylstannyl)methyl Acetate (6i). Colorless oil;
IR (neat): 3056, 2955, 2926, 2871, 2852, 1725, 1631, 1600, 1507,
1463 cm−1; 1H NMR (400 MHz, CDCl3): δ = 7.77 (t, J = 7.2 Hz, 3H),
7.53 (s, 1H), 7.46−7.36 (m, 2H), 7.24−7.21 (m, 1H), 6.08 (s, 1H),
2.19 (s, 3H), 1.45−1.31 (m, 6H), 1.26−1.19 (m, 6H), 0.92−0.75 (m,
15H) ppm; 13C NMR (125 MHz, CDCl3): δ = 170.9, 140.4, 133.7,
131.6, 128.1, 127.7, 127.4, 126.1, 124.9, 123.1, 120.9, 73.6, 28.8, 27.3,
21.1, 13.6, 10.1 ppm. HRMS (EI): m/z calcd for C21H29O2Sn [M −
Bu+]: 433.1190. Found: 433.1183.
2-Thienyl(tributylstannyl)methyl Acetate (6k). Pale yellow oil;
IR (neat): 2956, 2925, 2871, 2853, 1725, 1464, 1371, 1295, 1245,
1
1074 cm−1; H NMR (500 MHz, CDCl3): δ = 7.12 (d, J = 4.6 Hz,
1H), 6.91 (dd, J = 3.4, 4.6 Hz, 1H), 6.74 (d, J = 3.4 Hz, 1H), 6.07 (s,
1H), 2.10 (s, 3H), 1.47−1.41 (m, 6H), 1.30−1.23 (m, 6H), 0.92−0.85
(m, 15H) ppm; 13C NMR (125 MHz, CDCl3): δ = 170.7, 146.1,
126.7, 123.1, 122.0, 68.5, 28.8, 27.3, 20.9, 13.6, 10.3 ppm. HRMS (EI):
m/z calcd for C15H25O2SSn [M − Bu+]: 389.0597. Found: 389.0585.
(E)-1-(Tributylstannyl)-2-methyl-3-phenylallyl Acetate (6l).
Colorless oil; IR (neat): 2956, 2926, 2871, 2853, 1724, 1643, 1598,
1492, 1463, 1370 cm−1; 1H NMR (500 MHz, CDCl3): δ = 7.32 (dd, J
= 5.3, 7.3 Hz, 2H), 7.25 (d, J = 5.3 Hz, 2H), 7.18 (t, J = 7.3 Hz, 1H),
6.30 (s, 1H), 5.42 (s, 1H), 2.14 (s, 3H), 1.86 (s, 3H), 1.58−1.50 (m,
6H), 1.36−1.27 (m, 6H), 1.04−0.86 (m, 15H) ppm; 13C NMR (125
MHz, CDCl3): δ = 170.5, 138.1, 128.81, 128.78, 128.0, 125.7, 119.5,
76.3, 28.9, 27.4, 21.0, 16.1, 13.7, 10.3 ppm. HRMS (EI): m/z calcd for
C20H31O2Sn [M − Bu+]: 423.1346. Found: 423.1348.
55.2, 28.8, 27.5, 26.2, 24.5, 13.6, 11.2 ppm. HRMS (ESI): m/z calcd
for C24H45O2NSSnNa [M + Na]+: 554.2091. Found: 554.2079.
Synthesis of α-Acetoxy Stannanes. α-Acetoxy stannanes (6aa
and 6b−6l) were prepared according to a reported method.6l α-
Acetoxy stannane 6m was prepared according to a reported method.20
α-Acetoxy stannane 6n was prepared by the reaction of LiSnBu3 and
acetophenone at −78 °C. 6aa,12c 6b,12c 6e,12c and 6j21 are known
compounds.
Tributyl(3,4-dihydro-1H-isochromen-1-yl)stannane (6m).
Colorless oil; IR (neat): 2955, 2851, 1601, 1488, 1457, 1418, 1376,
4-Chlorophenyl(tributylstannyl)methyl Acetate (6c). Color-
1
1339, 1291, 1270 cm−1; H NMR (500 MHz, C6D6): δ = 7.05−7.03
less oil; IR (neat): 2956, 2926, 2871, 2853, 1726, 1594, 1489, 1370,
1
1246, 1091 cm−1; H NMR (500 MHz, CDCl3): δ = 7.25 (d, J = 7.3
(m, 1H), 6.93−6.92 (m, 2H), 6.84 (d, J = 8.0 Hz, 1H), 5.52 (s, 1H),
3.84−3.80 (m, 1H), 3.61−3.57 (m, 1H), 2.73−2.67 (m, 1H), 2.56−
2.51 (m, 1H), 1.59−1.53 (m, 6H), 1.37−1.53 (m, 6H), 1.04−0.89 (m,
15H) ppm; 13C NMR (125 MHz, CDCl3): δ = 141.2, 130.8, 129.0,
125.9, 123.7, 122.1, 75.1, 65.4, 29.2, 29.0, 27.3, 13.6, 10.0 ppm. HRMS
(EI): m/z calcd for C17H27OSn [M − Bu+]: 367.1084. Found:
367.1077.
Hz, 2H), 7.04 (d, J = 7.3 Hz, 2H), 5.87 (s, 1H), 2.14 (s, 3H), 1.43−
1.37 (m, 6H), 1.28−1.21 (m, 6H), 0.88−0.82 (m, 15H) ppm; 13C
NMR (125 MHz, CDCl3): δ = 170.8, 139.6, 134.6, 129.0, 123.9, 73,4,
28.8, 27.3, 21.0, 13.6, 9.9 ppm. HRMS (EI): m/z calcd for
C17H26ClO2Sn [M − Bu+]: 417.0643 Found: 417.0632.
4-Fluorophenyl(tributylstannyl)methyl Acetate (6d). Color-
less oil; IR (neat): 2956, 2926, 2871, 2853, 1725, 1604, 1508, 1418,
1-Phenyl-1-(tributylstannyl)ethyl Acetate (6n). Colorless oil;
1
1370, 1227 cm−1; H NMR (400 MHz, CDCl3): δ = 7.09−6.96 (m,
IR (neat): 2955, 2871, 1717, 1493, 1369, 1266, 1230, 1070, 1033, 953
1
cm−1; H NMR (500 MHz, CDCl3): δ = 7.31−7.28 (m, 2H), 7.14−
4H), 5.86 (s, 1H), 2.13 (s, 3H), 1.43−1.35 (m, 6H), 1.28−1.19 (m,
6H), 0.89−0.80 (m, 15H) ppm; 13C NMR (125 MHz, CDCl3): δ =
170.8, 160.6 (d, JCF = 242.0 Hz), 138.6 (d, JCF = 3.6 Hz), 125.3 (d, JCF
= 7.3 Hz), 115.2 (d, JCF = 21.4 Hz), 72.7, 28.8, 27.3, 21.0, 13.6, 9.9
ppm. HRMS (EI): m/z calcd for C17H26FO2Sn [M − Bu+]: 401.0939.
Found: 401.0939.
7.11 (m, 3H), 2.16 (s, 3H), 1.83 (s, 3H), 1.39−1.19 (m, 12H), 0.92−
0.69 (m, 15H) ppm; 13C NMR (125 MHz, CDCl3): δ = 171.9, 147.1,
128.2, 125.1, 123.4, 81.7, 28.8, 27.5, 24.7, 21.5, 13.6, 11.6 ppm. HRMS
(EI): m/z calcd for C18H29O2Sn [M − Bu]+: 397.1190. Found:
397.1193.
4-Tolyl(tributylstannyl)methyl Acetate (6f). Colorless oil; IR
(neat): 2956, 2925, 2871, 2853, 1723, 1512, 1463, 1369, 1339, 1250
cm−1; 1H NMR (500 MHz, CDCl3): δ = 7.08 (d, J = 8.0 Hz, 2H), 7.00
(d, J = 8.0 Hz, 2H), 5.86 (s, 1H), 2.30 (s, 3H), 2.12 (s, 3H), 1.42−1.36
(m, 6H), 1.27−1.20 (m, 6H), 0.86−0.80 (m, 15H) ppm; 13C NMR
(125 MHz, CDCl3): δ = 170.8, 139.6, 134.6, 129.0, 123.9, 73.4, 28.8,
27.3, 21.0, 13.6, 9.9 ppm. HRMS (EI): m/z calcd for C18H29O2Sn [M
− Bu+]: 397.1190. Found: 397.1186.
Synthesis of Optically Active 8. (S)-N-(tert-Butylsulfonyl)-α-
(tributylstannyl)benzylamines (8a, 8b, 8c, and 8d) were prepared
according to a previously reported method.12b α-Amido stannanes (8a,
8c, and 8d) are known compounds.12b
(S)-N-(tert-Butylsulfonyl)-α-(tributylstannyl)-4-fluorobenzyl-
amine (8b). Colorless oil; IR (neat): 3280, 2956, 2926, 2871, 2853,
1603, 1507, 1458, 1303, 1125 cm−1; 1H NMR (500 MHz, CDCl3): δ =
7.03−6.95 (m, 4 H), 4.53 (d, J = 9.0 Hz, 1 H), 4.43 (d, J = 9.0 Hz, 1
2164
dx.doi.org/10.1021/jo202597p | J. Org. Chem. 2012, 77, 2159−2168