Methane → tert-butyl 5-(3-methoxyphenyl)-1,2,6b,7,8,10,11,11a-octahydro-9H-azepino[4,5-b][1,4]oxazino[2,3,4-hi]indole-9-carboxylate

HRID 51056Notes

Reaction equation

HRID 51056 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:8]3=[C:9]([O:11][CH2:12][CH2:13][N:7]3[CH:6]3[CH2:14][CH2:15][N:16]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[CH2:17][CH2:18][CH:5]23)[CH:10]=1.[CH3:26][O:27][C:28]1[CH:29]=[C:30](B(O)O)[CH:31]=[CH:32][CH:33]=1.C>>[CH3:26][O:27][C:28]1[CH:33]=[C:32]([C:2]2[CH:3]=[C:4]3[C:8]4=[C:9]([O:11][CH2:12][CH2:13][N:7]4[CH:6]4[CH2:14][CH2:15][NH:16][CH2:17][CH2:18][CH:5]34)[CH:10]=2)[CH:31]=[CH:30][CH:29]=1.[CH3:26][O:27][C:28]1[CH:33]=[C:32]([C:2]2[CH:3]=[C:4]3[C:8]4=[C:9]([O:11][CH2:12][CH2:13][N:7]4[CH:6]4[CH2:14][CH2:15][N:16]([C:19]([O:21][C:22]([CH3:23])([CH3:25])[CH3:24])=[O:20])[CH2:17][CH2:18][CH:5]34)[CH:10]=2)[CH:31]=[CH:30][CH:29]=1

Participants

5

Reactant 3

HCID 297MethaneHCID 2734370(3-Methoxyphenyl)boronic acidHCID 22735371tert-butyl 5-bromo-1,2,6b,7,8,10,11,11a-octahydro-9H-azepino[4,5-b][1,4]oxazino[2,3,4-hi]indole-9-carboxylate

Product 2

HCID 22735631tert-butyl 5-(3-methoxyphenyl)-1,2,6b,7,8,10,11,11a-octahydro-9H-azepino[4,5-b][1,4]oxazino[2,3,4-hi]indole-9-carboxylateYield 139.7%HCID 227357875-(3-methoxyphenyl)-1,2,7,8,9,10,11,11a-octahydro-6bH-azepino[4,5-b][1,4]oxazino[2,3,4-hi]indole

Procedure

Tert-butyl 5-(3-methoxyphenyl)-1,2,6b,7,8,10,11,11a-octahydro-9H-azepino[4,5-b][1,4]oxazino[2,3,4-hi]indole-9-carboxylate (502 mg, 70%) was prepared via coupling of tert-butyl 5-bromo-1,2,6b,7,8,10,11,11a-octahydro-9H-azepino[4,5-b][1,4]oxazino[2,3,4-hi]indole-9-carboxylate (671 mg, 1.64 mmol) with 3-methoxyphenyl boronic acid (374 mg, 2.46 mmol) as illustrated by the general procedure described in Example 534 Step C. CIMS (Methane) m/z=437 [MH]+. The corresponding hydrochloride salt of the title compound was formed from tert-butyl 5-(3-methoxyphenyl)-1,2,6b,7,8,10,11,11a-octahydro-9H-azepino[4,5-b][1,4]oxazino[2,3,4-hi]indole-9-carboxylate (500 mg) using the procedure described in Example 534 Step D. Then, this salt was free-based using 6 N NaOH, to give the title compound (395 mg, 99%). 1H NMR (CDCl3, 500 MHz) δ1.80-2.30 (m, 4H), 2.75-2.98 (m, 3H), 3.00-3.12 (m, 1H), 3.13-3.29 (m, 2H), 3.43-3.53 (m, 1H), 3.63-3.78 (m, 1H), 3.85 (s, 3H), 4.11 (brs, 1H), 4.41 (brs, 2H), 6.82 (dd, 1H, J=0.8, 8.3 Hz), 6.88 (s, 1H), 6.90 (s, 1H), 7.02 (s, 1H), 7.10 (d, 1H, J=8.3 Hz), 7.30 (t, 1H, J=8.3 Hz) ppm. CIMS (Methane) m/z=337 [MH]+.

Sources & evidence

ORD record
ord-066ef8ad1c62451f8170e2fe5919f3d8
Source dataset
uspto-grants-2004_03
Patent number
US06713471B1

Reaction notes

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