10.1002/adsc.202000151
Advanced Synthesis & Catalysis
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J = 7.6 Hz, 2H), 5.95 (dq, J = 10.4, 5.6 Hz, 1H), 5.38
(d, J = 17.2 Hz, 1H), 5.27 (d, J = 10.4 Hz, 1H), 4.68
(d, J = 5.6 Hz, 2H), 4.23 (t, J = 8.4 Hz, 1H), 3.71–
3.60 (m, 1H), 2.43 (s, 3H), 2.16–2.00 (m, 2H), 1.84 (d,
J = 7.6 Hz, 2H), 1.70–1.54 (m, 4H), 1.55–1.45 (m,
1H), 1.44–1.37 (m, 1H), 1.29–1.21 (m, 1H), 1.13 (t, J
= 12.4 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 172.3,
143.5, 135.8, 131.8, 129.6, 127.6, 118.4, 65.9, 60.6,
60.3, 37.4, 32.9, 29.6, 25.7, 23.7, 21.6, 20.3; IR (KBr)
(v/cm−1): 3446, 2830, 1631, 1362, 1076, 786; HRMS
(ESI) calcd for C19H26NO4S [M+H]+ 364.1577, found
364.1576; HPLC (Daicel Chiralcel OD-H, n-hexane/i-
PrOH = 80/20, UV = 210 nm, flow rate = 1.0
mL/min) tR1 = 5.863 min (major) and tR2 = 7.365 min
(minor), ee = 94%; [α]2D5 = –46.3 (c 0.41, CHCl3).
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The synthesis of Allyl(2S,3aS,7aS)-octahydro-1H-
indole-2-carboxylate (11)[19]
Pre-activated magnesium was added to a solution of
10 (0.2 mmol) in MeOH (2.0 mL) and stirred
o
vigorously at 30 C for 8 h. Then the reaction was
quenched by 1N HCl aq. (1.0 mL) and basified with
saturated NaHCO3. The organic layer was extracted
with EtOAc (6 mL × 3), washed with brine, and dried
over Na2SO4. The organic layer was concentrated and
the residue was purified by silica gel column
chromatography (PE/EtOAc/Et3N = 1/1/0.02) to give
allyl (2S,3aS,7aS)-octahydro-1H-indole-2-carboxylate
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1
11 as a colorless oil (25.9 mg, 62%). H NMR (400
MHz, CDCl3) δ 5.88 (ddt, J = 17.2, 10.4, 5.6 Hz, 1H),
5.28 (dq, J = 17.2, 1.6 Hz, 1H), 5.20 (ddd, J = 10.4,
2.4, 1.2 Hz, 1H), 4.67–4.51 (m, 2H), 3.79 (dd, J =
10.0, 6.0 Hz, 1H), 3.05 (q, J = 5.2 Hz, 1H), 2.30 (s,
1H), 2.15 (ddd, J = 12.8, 10.0, 6.8 Hz, 1H), 2.06–1.90
(m, 1H), 1.65 (dddd, J = 15.6, 13.1, 10.4, 5.0 Hz, 3H),
1.53–1.38 (m, 3H), 1.36–1.28 (m, 1H), 1.25–1.11 (m,
2H); 13C NMR (100 MHz, CDCl3) δ 175.6, 131.9,
118.4, 65.5, 58.6, 58.1, 37.9, 35.8, 28.0, 27.1, 23.5,
21.5; IR (KBr) (v/cm−1): 3418, 2827, 2856, 1733,
1192; HRMS (ESI) calcd for C12H20NO2 [M+H]+
210.1489, found 210.1487; HPLC (Daicel Chiralcel
OD-H, n-hexane/i-PrOH = 92/8, UV = 210 nm, flow
rate = 1.0 mL/min) tR1 = 5.145 min (major) and tR2
=
6.070 min (minor), ee = 92%; [α]2D5 = –40.0 (c 0.5,
CHCl3).
Acknowledgements
This work was supported by National Natural Science Foundation
of China (No. 21672142, 21971162, 21831005 and 21620102003)
and Shanghai Munici-pal Education Commission (No.
201701070002E00030).
References
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11
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