3422
X. Bian et al.
LETTER
removing the solvent, the residue was subjected to
chromatography to give allyl amine 11. The dr was
determined by 1H NMR analysis of crude 11. The absolute
configuration of amine in 11 was not determined due to lack
of comparable rotation data of structurally similar chiral
amine.
62.6, 63.6, 135.5, 149.1, 165.5, 170.7, 171.1. HRMS: m/z [M
+ H+] calcd for C16H28NO5S: 346.1682; found: 346.1685.
Data for 8e (major isomer): 1H NMR (400 MHz, CDCl3):
d = 1.15 (s, 9 H), 1.72–1.82 (m, 2 H), 2.42–2.50 (m, 2 H),
2.70–2.84 (m, 2 H), 3.44–3.54 (m, 4 H), 4.47 (s, 2 H), 4.48
(s, 2 H), 6.30 (t, J = 7.6 Hz, 1 H), 7.24–7.38 (m, 10 H), 8.06
(s, 1 H). 13C NMR (50 MHz, CDCl3): d = 22.4, 25.8, 26.5,
26.7, 57.0, 68.4, 69.2, 72.5, 72.6, 127.4, 127.5, 126.2, 126.3,
135.7, 138.3, 149.8, 165.7. HRMS: m/z [M + H+] calcd for
C26H36NOS: 442.2410; found: 442.2422.
Data for 11a (major isomer): [a]20D +11.9 (c = 1.0, CHC13).
1H NMR (400 MHz, CDCl3): d = 1.14 (s, 9 H), 2.32 (s, 3 H),
2.43–2.50 (m, 2 H), 2.71 (t, J = 7.6 Hz, 2 H), 3.10 (d, J = 15.6
Hz, 1 H), 3.26 (d, J = 4.0 Hz, 1 H), 3.40 (d, J = 15.6 Hz, 1
H), 4.82 (d, J = 4.0 Hz, 1 H), 5.89 (t, J = 7.2 Hz, 1 H), 6.94
(d, J = 6.8 Hz, 2 H), 7.09–7.30 (m, 12 H). 13C NMR (50
MHz, CDCl3): d = 21.1, 22.6, 30.0, 34.1, 35.7, 55.7, 63.1,
125.7, 125.9, 127.5, 128.3, 128.3, 128.5, 129.2, 129.5,
137.4, 137.8, 138.1, 139.3, 141.6. HRMS: m/z [M + H+]
calcd for C29H36NOS: 446.2512; found: 446.2521.
Date for 11b (major isomer): [a]20D +33.5 (c = 1.0, CHC13).
1H NMR (400 MHz, CDCl3): d = 1.15 (s, 9 H), 1.28 (s, 3 H),
2.42–2.48 (m, 2 H), 2.73 (t, J = 7.6 Hz, 2 H), 2.91 (d, J = 5.6
Hz, 1 H), 3.41 (dd, J1 = 23.2 Hz, J2 = 15.6 Hz, 2 H), 3.88 (m,
1 H), 5.73 (t, J = 7.6 Hz, 1 H), 7.08 (d, J = 7.2 Hz, 2 H), 7.16–
7.35 (m, 8 H). 13C NMR (50 MHz, CDCl3): d = 22.4, 22.6,
30.2, 33.4, 35.7, 55.5, 56.8, 125.9, 126.0, 128.3, 128.4,
128.5, 139.1, 139.7, 141.7. HRMS: m/z [M + H+] calcd for
C23H32NOS: 370.2199; found: 370.2210.
Data for 4g (major isomer): 1H NMR (400 MHz, CDCl3):
d = 1.55–1.70 (m, 6 H), 2.30–2.42 (m, 4 H), 3.42–3.51 (m, 4
H), 4.48 (s, 2 H), 4.49 (s, 2 H), 6.47 (t, J = 7.6 Hz, 1 H), 7.25–
7.36 (m, 10 H), 9.36 (s, 1 H). 13C NMR (50 MHz, CDCl3):
d = 20.7, 25.4, 26.5, 26.6, 26.7, 29.4, 69.7, 69.8, 72.8, 72.9,
127.4, 127.5, 127.6, 128.3, 128.4, 138.4, 138.5, 143.2,
155.3, 195.1. HRMS: m/z [M + Na+] calcd for C24H30NaO3:
389.2087; found: 389.2089.
Data for 4h (major isomer): 1H NMR (400 MHz, CDCl3):
d = 1.38–1.57 (m, 6 H), 1.57–1.70 (m, 4 H), 2.25 (t, J =
7.6 Hz, 2 H), 2.34 (q, J = 7.2 Hz, 2 H), 3.42–3.50 (m, 4 H),
4.48 (s, 2 H), 4.50 (s, 2 H), 6.43 (t, J = 7.6 Hz, 1 H), 7.24–
7.38 (m, 10 H), 9.35 (s, 1 H). 13C NMR (50 MHz, CDCl3):
d = 23.7, 25.3, 26.0, 28.5, 28.7, 29.5, 29.6, 70.1, 72.8, 76.4,
77.0, 77.7, 127.4, 127.5, 127.6, 128.3, 128.4, 138.3, 138.4,
143.5, 155.3, 195.2. HRMS: m/z [M + Na+] calcd for
C26H34NaO3: 417.2400; found: 417.2388.
Date for 11c (major isomer): [a]20D +34.0 (c = 1.0, CHC13).
1H NMR (400 MHz, CDCl3): d = 0.77 (d, J = 6.8 Hz, 3 H),
0.90 (d, J = 6.8 Hz, 3 H), 1.07 (s, 9 H), 1.70–1.74 (m, 1 H),
2.44–2.50 (m, 2 H), 2.68–2.72 (m, 2 H), 3.12 (d, J = 3.6 Hz,
1 H), 3.31–3.41 (m, 2 H), 3.43–3.44 (m, 1 H), 5.63 (t, J = 7.2
Hz, 1 H), 7.10–7.28 (m, 10 H). 13C NMR (100 MHz, CDCl3):
d = 18.6, 20.0, 22.3, 30.2, 30.9, 33.7, 35.6, 55.2, 67.3, 76.5,
76.8, 77.2, 125.7, 125.8, 128.1, 128.3, 128.5, 130.7, 136.5,
139.4, 141.5. HRMS: m/z [M + Na+] calcd for
Data for 10 (Z major isomer): 1H NMR (400 MHz, CDCl3):
d = 0.98 (s, 9 H), 4.06 (dd, J1 = 19.6 Hz, J2 = 15.2 Hz, 2 H),
7.14–7.31 (m, 5 H), 7.41 (s, 1 H), 7.57 (d, J = 8.8 Hz, 2 H),
8.21 (d, J = 9.2 Hz, 2 H), 8.36 (s, 1 H). 13C NMR (100 MHz,
CDCl3): d = 22.3, 32.6, 57.8, 123.9, 126.4, 127.9, 128.7,
129.9, 138.2, 140.3, 141.6, 142.2, 147.6, 165.0. HRMS:
m/z [M + Na+] calcd for C20H22N2NaO3S: 393.1243; found:
393.1235. Data for 10 (E minor isomer): 1H NMR (400
MHz, CDCl3): d = 0.98 (s, 9 H), 4.16 (dd, J1 = 24.8 Hz,
J2 = 16.4 Hz, 2 H), 7.35 (d, J = 8.4 Hz, 2 H), 7.38–7.42 (m,
5 H), 7.46 (s, 1 H), 8.14 (d, J = 8.8 Hz, 2 H), 8.36 (s, 1 H).
C25H35NNaOS: 420.2332; found: 420.2337.
Date for 11d (major isomer): [a]20D +15.3 (c = 1.0, CHC13).
1H NMR (400 MHz, CDCl3): d = 0.92 (s, 9 H), 1.07 (s, 9 H),
2.32–2.42 (m, 2 H), 2.65 (t, J = 8.0 Hz, 2 H), 3.24–3.28 (m,
2 H), 3.56–3.60 (m, 2 H), 5.63 (t, J = 7.2 Hz, 1 H), 7.10 (d,
J = 6.8 Hz, 2 H), 7.14–7.30 (m, 8 H). 13C NMR (100 MHz,
CDCl3): d = 22.3, 27.2, 29.5, 30.4, 35.4, 36.0, 55.2, 68.1,
125.6, 128.0, 128.1, 128.2, 128.6, 132.4, 139.1, 141.5.
HRMS: [M + H+] calcd for C26H38NOS: 412.2669; found:
412.2653.
(10) Representative Procedure of Grignard Addition to 8c:
To a solution of 8c (1 mmol) in anhyd CH2Cl2 (10 mL) at
0 °C was added Grignard reagent (3 equiv). After being
stirred for 1–5 h, the mixture was poured into sat. NH4Cl
solution, and the solution was extracted with CH2Cl2. The
combined organic phases were dried with Na2SO4. After
Synlett 2006, No. 20, 3419–3422 © Thieme Stuttgart · New York