Tributylstannane → methyl 3-(tert-butoxycarbonyl)-1-(chloromethyl)-1,2-dihydro-3H-benzo[e]indole-7-carboxylate

HRID 2238401Notes

Reaction equation

HRID 2238401 reaction equation
[C:1]([O:5][C:6]([N:8]([CH2:24][CH:25]=[CH:26][Cl:27])[C:9]1[CH:18]=[CH:17][C:16]2[C:11](=[CH:12][CH:13]=[C:14]([C:19]([O:21][CH3:22])=[O:20])[CH:15]=2)[C:10]=1Br)=[O:7])([CH3:4])([CH3:3])[CH3:2].CCCC[SnH](CCCC)CCCC.CC(N=NC(C#N)(C)C)(C#N)C>C1C=CC=CC=1>[C:1]([O:5][C:6]([N:8]1[C:9]2[CH:18]=[CH:17][C:16]3[CH:15]=[C:14]([C:19]([O:21][CH3:22])=[O:20])[CH:13]=[CH:12][C:11]=3[C:10]=2[CH:25]([CH2:26][Cl:27])[CH2:24]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 5948TributylstannaneHCID 6547AzobisisobutyronitrileHCID 75066180Methyl 2-[(tert-butoxycarbonyl)(3-chloro-2-propen-1-yl)amino]-1-bromo-6-naphthoate

Product 1

HCID 44550493methyl 3-(tert-butoxycarbonyl)-1-(chloromethyl)-1,2-dihydro-3H-benzo[e]indole-7-carboxylateYield 85.2%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

A mixture of 149 (1.16 g, 2.55 mmol), Bu3SnH (0.69 mL, 2.56 mmol) and AIBN (50 mg, 0.30 mmol) in dry benzene (15 mL) under N2 was stirred at reflux for 2 h, then concentrated under reduced pressure. The residue was triturated with i-Pr2O and the resulting solid was purified by chromatography on silica gel, eluting with CH2Cl2/EtOAc (19:1), to give methyl 3-(tert-butoxycarbonyl)-1-(chloromethyl)-1,2-dihydro-3H-benzo[e]indole-7-carboxylate (150) (817 mg, 85%) as a white solid. mp EtOAc) 187-189° C.; 1H NMR [(CD3)2SO] δ 8.60 (d, J=1.2 z, 1H), 8.1 (v br, 1H), 8.09 (d, J=8.6 Hz, 1H), 8.00 (d, J=8.8 Hz, 1H), 7.97 (dd, J=8.8, 1.6 Hz, 1H), 4.31-4.23 (m, 1H), 4.20 (t, J=10.4 Hz, 1H), 4.09 (dd, J=11.2, 2.5 Hz, 1H), 4.04 (dd, J=11.1, 3.1 Hz, 1H), 3.96-3.88 (m, 4H), 1.55 (s, 9H). Anal. (C20H22ClNO4) C, H, N.

Workup

  1. temperatureat reflux for 2 h
  2. concentrationconcentrated under reduced pressure
  3. customThe residue was triturated with i-Pr2O
  4. customthe resulting solid was purified by chromatography on silica gel
  5. washeluting with CH2Cl2/EtOAc (19:1)

Sources & evidence

ORD record
ord-9d8a50829f48449d8897ec348e0e706a
Source dataset
uspto-grants-2010_05
Patent number
US07718688B2

Reaction notes

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