H. Li et al. / Journal of Organometallic Chemistry 696 (2011) 316e320
319
154.8, 145.2, 144.7, 140.5, 132.2, 128.7, 128.5, 126.7, 126.6, 126.5,
126.4, 121.2, 117.6, 114.1, 59.6, 55.5, 51.9, 46.4. IR (neat, cmꢃ1): 2930,
1650, 1531, 1512, 1367, 1235, 1034, 827, 701. Anal. calcd (found) for
C26H26N2O2: H, 6.58 (6.77); C, 78.36 (78.26).
36.3, 34.6, 26.0, 23.7, 22.9. IR (neat, cmꢃ1): 2924, 1664, 1543, 1499,
1328, 1250, 1113, 854, 752, 609. Anal. calcd (found) for C18H23N3O3:
H, 7.04 (7.05); C, 65.63 (65.42).
4.2.11. N-(4-Nitrophenyl)-2-vinylpyrrolidine-1-carboxamide (Table
2, entry 11)
4.2.6. N-(4-Methoxybenzyl)-4,4-diphenyl-2-vinylpyrrolidine-1-
carboxamide (Table 2, entry 6)
Yellow solid, 82%. TLC (hexaneseEtOAc ¼ 1:1): Rf ¼ 0.5. 1H NMR:
White solid, 89%. TLC (hexaneseEtOAc ¼ 1:1): Rf ¼ 0.45. 1H
d
8.12 (d, J ¼ 9.2 Hz, 2H), 7.49 (d, J ¼ 9.2 Hz, 2H), 6.88 (s,1H), 5.91 (m,
NMR:
d
7.29e7.13 (m,12H), 6.81 (d, J ¼ 8.4 Hz, 2H), 5.79 (m,1H), 5.19
1H), 5.35 (d, J ¼ 17.2 Hz, 1H), 5.12 (d, J ¼ 10.0 Hz, 1H), 4.28 (m, 1H),
3.64 (dt, J ¼ 7.2, 10.4 Hz, 1H), 3.54 (m, 1H), 2.25e2.17 (m, 1H),
(d, J ¼ 17.2 Hz, 1H), 5.12 (d, J ¼ 10.0 Hz, 1H), 4.95 (d, J ¼ 11.6 Hz, 1H),
4.82 (t, J ¼ 5.6 Hz, 1H), 4.35 (m, 2H), 3.84 (q, J ¼ 8.0 Hz, 1H), 3.78 (s,
1H), 3.62 (d, J ¼ 11.6 Hz,1H), 2.76 (q, J ¼ 6.4 Hz,1H), 2.53 (dd, J ¼ 9.6,
1.99e1.81 (m, 3H). 13C{1H} NMR:
d 153.2, 145.4, 142.2, 139.2, 125.1,
117.8, 116.7, 60.1, 47.0, 33.2, 22.9. IR (neat, cmꢃ1): 1658, 1501, 1328,
1251, 1112, 852, 751. Anal. calcd (found) for C13H15N3O3: H, 5.79
(5.85); C, 59.76 (59.39).
12.0 Hz, 1H). 13C{1H} NMR:
d 158.7, 157.3, 145.3, 144.9, 140.2, 131.7,
128.60, 128.56, 128.50, 126.8, 126.6, 126.5, 126.4, 117.0, 113.9, 59.2,
55.7, 55.3, 52.1, 46.4, 44.0. IR (neat, cmꢃ1): 2925, 1638, 1512, 1246,
1176, 1033, 701. Anal. calcd (found) for C27H28N2O2: H, 6.84 (6.74);
C, 78.61 (78.53).
4.2.12. 2-(2-Ethyloct-1-enyl)-N-(4-nitrophenyl)-4,4-
diphenylpyrrolidine-1-carboxamide (5)
Yellow solid, 93% as a 1.3:1 mixture of diastereomers. TLC
4.2.7. N-Butyl-4,4-diphenyl-2-vinylpyrrolidine-1-carboxamide
(Table 2, entry 7)
(hexaneseEtOAc ¼ 3:1): Rf ¼ 0.65. 1H NMR:
d 8.12 (m, 2H), 7.42 (m,
2H), 7.31e7.14 (m, 11H), [5.27 (d, J ¼ 9.2 Hz), 5.23 (d, J ¼ 9.2 Hz),
1.3:1, 1H], 4.95 (d, J ¼ 11.6 Hz, 1H), 4.28 (m, 1H), [3.73 (d,
J ¼ 12.0 Hz), 3.72 (d, J ¼ 12.0 Hz), 1.3:1, 1 H], 2.82 (m, 1H), 2.56 (m,
1H), 2.22e1.98 (m, 4H), 1.44e1.19 (m, 8H), [1.03 (t, J ¼ 7.6 Hz), 1.01
(t, J ¼ 7.6 Hz), 1.3:1, 3H], 0.84 (t, J ¼ 7.2 Hz, 3H). 13C{1H} NMR:
White solid, 90%. TLC (hexaneseEtOAc ¼ 3:1): Rf ¼ 0.4. 1H NMR:
d
7.29e7.14 (m, 10H), 5.80 (m, 1H), 5.25 (d, J ¼ 17.2 Hz, 1H), 5.17 (d,
J ¼ 10.4 Hz, 1H), 4.91 (dd, J ¼ 1.2, 11.6 Hz, 1H), 4.51 (t, J ¼ 5.6 Hz, 1H),
3.80 (q, J ¼ 8.0 Hz, 1H), 3.60 (d, J ¼ 11.2 Hz, 1H), 3.21 (m, 1H), 2.74
(dq, J ¼ 2.0, 6.0 Hz, 1H), 2.53 (dd, J ¼ 9.6, 12.0 Hz, 1H), 1.41 (m, 2H),
d
153.4, 147.7, 145.4, 145.1, 145.0, 144.4, 142.2, 129.1, 128.8, 128.6,
1.27 (m, 2H), 0.89 (t, J ¼ 7.6 Hz, 3H). 13C{1H} NMR:
d
157.5, 145.4,
126.7, 126.6, 126.4, 126.3, 125.2, 124.8, 117.6, 117.5, 55.3, 55.2, 54.2,
51.7, 46.3, 36.4, 31.9, 31.8, 31.6, 31.4, 30.6, 29.7, 29.2, 29.1, 28.8, 28.1,
22.5, 22.4, 14.0, 13.7, 12.7. IR (neat, cmꢃ1): 2928, 1680, 1541, 1503,
1327, 1253, 1112, 750, 699. Anal. calcd (found) for C33H39N3O3: H,
7.48 (7.26); C, 75.40 (75.27).
145.1, 140.5, 128.6, 128.5, 126.8, 126.6, 126.5, 126.3, 116.7, 59.3, 55.6,
52.0, 46.5, 40.2, 32.2, 20.0, 13.8. IR (neat, cmꢃ1): 2928, 1634, 1529,
1358, 1205, 756, 700. Anal. calcd (found) for C23H28N2O: H, 8.10
(8.14); C, 79.27 (79.12).
4.2.8. 2-(2-Methylprop-1-enyl)-N-(4-nitrophenyl)-4,4-
diphenylpyrrolidine-1-carboxamide (Table 2, entry 8)
Yellow solid, 91%. TLC (hexaneseEtOAc ¼ 3:1): Rf ¼ 0.4. 1H NMR:
4.3. Control experiments
d
8.13 (d, J ¼ 9.2 Hz, 2H), 7.41 (d, J ¼ 8.0 Hz, 2H), 7.31e7.17 (m, 10H),
4.3.1. Gold alone
7.14 (s, 1H), 5.31 (d, J ¼ 9.2 Hz, 1H), 4.97 (d, J ¼ 11.6 Hz, 1H), 4.24 (m,
1H), 3.66 (d, J ¼ 12.0 Hz, 1H), 2.81 (q, J ¼ 6.0 Hz, 1H), 2.54 (dd,
A solution of 1 (21.0 mg, 0.05 mmol), [(S)-2]Au2Cl2 (4.0 mg,
5 mol%), and n-hexadecane (11 mg, internal standard) in ether
(0.5 mL) was stirred at 23 ꢀC for 48 h. GC analysis of the crude
reaction mixture revealed neither detectable consumption of 1 nor
formation of 3.
J ¼ 9.6, 12.0 Hz, 1H). 13C{1H} NMR:
d 153.3, 145.4, 145.1, 144.5, 142.1,
137.7, 128.8, 128.6, 126.7, 126.64, 126.60, 126.4, 126.1, 125.2, 117.6,
55.1, 54.6, 51.7, 45.8, 26.0, 18.1. IR (neat, cmꢃ1): 2922, 1681, 1540,
1504, 1328, 1254, 1113, 699. Anal. calcd (found) for C27H27N3O3: H,
6.16 (6.20); C, 73.45 (73.60).
4.3.2. Silver alone
A solution of 1 (21.0 mg, 0.05 mmol), AgBF4 (1.0 mg, 10 mol%),
and n-hexadecane (11 mg, internal standard) in ether (0.5 mL) was
stirred at 23 ꢀC for 48 h. GC analysis of the crude reaction mixture
revealed neither detectable consumption of 1 nor formation of 3.
4.2.9. N-(4-Nitrophenyl)-5,5-diphenyl-2-vinylpiperidine-1-
carboxamide (Table 2, entry 9)
Yellow solid, 89%. TLC (hexaneseEtOAc ¼ 3:1): Rf ¼ 0.5. 1H NMR:
d
8.15 (d, J ¼ 9.2 Hz, 2H), 7.47 (d, J ¼ 9.2 Hz, 2H), 7.33e7.16 (m, 10H),
6.69 (s, 1H), 5.89 (m, 1H), 5.40 (dd, J ¼ 2.0, 10.8 Hz, 1H), 5.23 (dd,
J ¼ 2.0, 17.6 Hz, 1H), 5.10 (dd, J ¼ 2.0, 14.0 Hz, 1H), 4.48 (m, 1H), 3.10
(d, J ¼ 14.0 Hz, 1H), 2.49 (dq, J ¼ 2.8, 13.2 Hz, 1H), 2.36 (dt, J ¼ 4.0,
4.3.3. Silver and ligand
A solution of 1 (21.0 mg, 0.05 mmol), AgBF4 (1.0 mg, 10 mol %),
(S)-2 (3.0 mg, 5 mol %), and n-hexadecane (11 mg, internal stan-
dard) in ether (0.5 mL) was stirred at 23 ꢀC for 48 h. GC analysis of
the crude reaction mixture revealed neither detectable consump-
tion of 1 nor formation of 3.
12.8 Hz, 1H), 1.85e1.77 (m, 2H). 13C{1H} NMR (125 MHz):
d 154.3,
147.1, 145.3, 144.2, 135.3, 128.6, 128.5, 127.7, 126.6, 126.2, 125.0,
118.6, 117.5, 53.5, 48.0, 46.3, 29.9, 25.9. IR (neat, cmꢃ1): 1724, 1654,
1501, 1330,1251, 1112, 752, 701. HRMS calcd (found) for C26H26N3O3
(MHþ): 428.1974 (428.1987). Anal. calcd (found) for C26H25N3O3: H,
5.89 (5.84); C, 73.05 (72.79).
Acknowledgements
4.2.10. N-(4-Nitrophenyl)-3-vinyl-2-aza-spiro[4.5]decane-2-
carboxamide (Table 2, entry 10)
The authors thank the NIH (GM-080422) for support of this
research.
Yellow solid, 76%. TLC (hexaneseEtOAc ¼ 3:1): Rf ¼ 0.3. 1H NMR:
d
8.12 (m, 2H), 7.49 (m, 2H), 7.09 (s, 1H), 5.94 (m, 1H), 5.47 (d,
J ¼ 17.2 Hz,1H), 5.36 (d, J ¼ 10.0 Hz,1H), 4.26 (q, J ¼ 8.0 Hz,1H), 3.80
(d, J ¼ 11.2Hz, 1H), 3.14 (d, J ¼ 11.2 Hz, 1H), 2.15 (dq, J ¼ 1.2, 7.2 Hz,
1H), 1.62 (dd, J ¼ 8.8, 12.8 Hz, 1H), 1.50e1.32 (m, 10H). 13C{1H} NMR:
Supplementary data
Supplementary data related to this article can be found online at
d
153.6, 145.4, 142.2, 140.9, 125.1, 117.7, 117.2, 59.8, 56.9, 45.6, 40.5,