LETTER
Synthesis and Reactivity of New Chiral 1-[(Trialkylsilyl)methyl]propenamides
1893
Kingsbury, J. S.; Harrity, J. P. A. Org. Biomol. Chem. 2004,
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1978, 19, 3043. (c) Sarker, T. K.; Andersen, N. H.
Tetrahedron Lett. 1978, 19, 3513. (d) Deleris, G.;
Dunogues, J.; Calas, R.; Pisciotti, F. J. Organomet. Chem.
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Pisciotti, F. J. Organomet. Chem. 1975, 93, 43. (f) Able, E.
W.; Rowley, R. J. J. Organomet. Chem. 1975, 84, 199.
(g) Hosomi, A.; Sakurai, H. Tetrahedron Lett. 1976, 1295.
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2, 8. (i) Brümmer, O.; Rückert, A.; Blechert, S. Chem. Eur.
J. 1997, 3, 441. (j) Vernall, A. J.; Abell, A. D. Aldrichimica
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(2) Kingsbury, J. S.; Harrity, J. P. A.; Bonitatebus, P. J.;
Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 791.
(3) Garber, S. B.; Kingsbury, J. S.; Gray, B. L.; Hoveyda, A. H.
J. Am. Chem. Soc. 2000, 122, 8168.
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41, 9973.
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63, 6088.
(7) Choi, T.-L.; Chatterjee, A. K.; Grubbs, R. H. Angew. Chem.
Int. Ed. 2001, 40, 1277.
(16) Spectroscopic Data for Compound 15
Major isomer(syn): 1H NMR (300 MHz, CDCl3): d = 7.26–
7.08 (m, 10 H), 6.31 (d, J = 7.5 Hz, 1 H, NH amide), 5.90 (m,
1 H), 5.27 (d, J = 10.2 Hz, 1 H), 5.17 (d, J = 17.1 Hz, 1 H),
4.79 (m, 1 H), 4.17–4.10 (m, 3 H), 3.31 (br s, 1 H, OH), 3.15
(m, 2 H), 2.82 (dd, J = 7.5, 3.2 Hz, 1 H), 1.28 (t, J = 7.2 Hz,
1 H), 1.12 (d, J = 6.4 Hz, 1 H). 13C NMR (75 MHz, CDCl3):
d = 171.7 (s), 171.5 (s), 135.9 (s), 132.1 (d), 129.3 (2 d),
128.6 (2 d), 127.2 (d), 121.0 (t), 67.5 (d), 61.7 (q), 57.5 (d),
53.1 (d), 37.8 (t), 19.9 (q),14.2 (q). IR (neat): n = 3367, 3306,
2978, 2929, 1724, 1632, 1545, 1279, 1180 cm–1. HRMS:
m/z calcd for C17H24NO4 [M]: 306.1705 [M + H+]; found:
306.1711.
(8) Streuff, J.; Nieger, M.; Muñiz, K. Chem. Eur. J. 2006, 12,
4362.
(9) Compounds 1–4, and 4¢ were prepared from commercially
available chiral L-amino esters and acryloyl chloride in the
presence of Et3N at 0 °C
(10) Two separated spots appear corresponding to the two
isomers E and Z. The E/Z ratio is greater than 14:1.
(11) Spectroscopic Data for Compound 13
1H NMR (300 MHz, CDCl3): d = 6.95 (td, J = 8.8, 15.1 Hz,
1 H), 6.87 (d, J = 8.3 Hz, 1 H, NH), 6.45 (d, J = 7.2 Hz, 1 H,
NH), 6.36 (d, J = 16.9 Hz, 1 H), 6.23 (m, 1 H), 5.73 (d,
J = 14.9 Hz, 1 H), 5.68 (d, J = 9.8 Hz, 1 H) 4.95 (m, 2 H),
3.72 (s, 6 H), 3.37–3.11 (m, 4 H), 1.70 (d, J = 8.8 Hz, 4 H),
0.01 (s, 9 H). 13C NMR (75 MHz, CDCl3): d = 171.2 (s),
170.9 (s), 165.9 (s), 165.3 (s), 145.1 (d), 130.2 (d), 127.8 (t),
120.6 (d), 52.9 (2 q), 51.8 (d), 51.7 (d), 41.2 (t), 41.0 (t), 24.7
(t), –1.7 (3 q). IR (neat): n = 3320, 2955, 2890, 1741, 1659,
1214, 1186 cm–1. MS: m/z = 463 (23)[M+ + 1], 405 (64), 391
(100) [M – SiMe3], 377 (17), 313 (9), 276 (20), 242 (7), 204
(56), 190 (25), 170 (20), 156 (7), 142 (1.6), 86 (2). HRMS:
m/z calcd for C18H31N2O6S2Si [M]: 463.1393 [M + H+];
found: 463.1404.
(17) The identities of the syn and anti products were readily
established from their 1H NMR spectra. The a-products were
distinguished by virtue of the larger vicinal coupling
constant of the a-methine proton in the anti diastereomer
(J = 7–8 Hz) relative to the syn diastereomer (J = 3.2 Hz,
Figure 3).
H
H
HO
R
H
HO
R
H
O
O
H
H
J = 3.2 Hz
J = 7–8 Hz
N
N
EtO
EtO
O
O
Ph
Ph
syn-15
anti-15
(12) Spectroscopic Data for Compound 14
Figure 3
E/E-Isomers: 1H NMR (300 MHz, CDCl3): d = 6.92 (td,
J = 8.8, 14.9 Hz, 2 H), 6.60 (d, J = 7.5 Hz, 2 H, NH), 5.71 (d,
J = 15.0 Hz, 2 H), 4.92 (m, 2 H), 3.71 (s, 6 H), 3.15 (ddd,
J = 5.9, 14.1, 21.8 Hz, 4 H), 1.65 (d, J = 8.7 Hz, 4 H), 0.01
(s, 18 H). E/E-Isomers: 13C NMR (75 MHz, CDCl3): d =
171.1 (2 s), 165.8 (2 s), 144.7 (2 d), 120.6 (2 d), 52.7 (2 q),
51.5 (2 d), 41.1 (2 t), 24.5 (2 t), –1.8 (6 q). E/Z-Isomers: 1H
NMR (300 MHz, CDCl3): d = 6.92 (td, J = 8.7, 15.1 Hz, 1
HE), 6.51 (d, J = 7.5 Hz, 1 H, NH), 6.49 (d, J = 7.3 Hz, 1 H,
NH), 6.26 (dd, J = 9.6, 10.7 Hz, 1 HZ), 5.70 (d, J = 15.1 Hz,
1 HE), 5.62 (d, J = 11.3 Hz, 1 HZ), 3.73 (s, 6 H), 3.15 (m, 4
H), 2.35 (m, 2 H), 1.65 (d, J = 8.8 Hz, 2 H), 0.01 (s, 18 H).
E/Z-Isomers: 13C NMR (75 MHz, CDCl3): d = 171.2 (s),
171.1 (s), 166.6 (s), 165.8 (s), 146.2 (d), 144.9 (d), 120.6 (d),
117.7 (d), 120.6 (d), 52.8 (q), 52.7 (q), 51.6 (d), 51.2 (d),
41.1 (2 t), 24.6 (t), 22.7 (t), –1.6 (3 q), –1.7 (3 q). IR (neat):
n = 3320, 2955, 2890, 1745, 1656, 1214, 1186 cm–1. MS:
m/z = 549 (100)[M+ + 1], 477 (8), 276 (22), 242 (6), 204 (2),
170 (1.6), 142 (3), 73 (3). HRMS: m/z calcd for
(18) Separation of syn and anti isomers was achieved by
Supercritical Fluid Chromatography (column: AD-
H21 × 250, mobile phase 15% EtOH, parameters: F = 50
mL/min, nozzle pressure: 100 bar).
(19) When the reaction is not complete and when the aldehyde
contains traces of water, protodesilylation product 23 is
formed (Figure 4).
O
H
N
R2O
O
R1
23
Figure 4
C22H41N2O6S2Si2 [M]: 549.1945 [M + H+]; found: 549.1976.
(13) (a) Majewski, M.; Mpango, G. B.; Thomas, M. T.; Wu, A.;
Snieckus, V. J. Org. Chem. 1981, 46, 2029. (b) Green, J.
R.; Snieckus, V. Tetrahedron Lett. 1986, 27, 535.
(c) Green, J. R.; Alo, B. I.; Majewski, M.; Snieckus, V. Can.
J. Chem. 2009, 87, 745; and references cited therein.
(20) General Procedure for the One-Pot Process
To a solution of allyltrimethylsilane (1.1 equiv) and
acrylamide 1 (1 mmol) in dry THF (5 mL/mmol) under an
argon atmosphere was added Hoveyda–Grubbs catalyst II.
After 2 h at r.t. the aldehyde was introduced (1.3 equiv), the
temperature reduced to –78 °C, and TBAF (1.1 equiv) was
added. After 10 min, the reaction mixture was washed with
NH4Cl, dried over MgSO4, and concentrated carefully at r.t.
Synlett 2011, No. 13, 1888–1894 © Thieme Stuttgart · New York