Tributylstannane → HCID 44550374, compound

HRID 2238408Notes

Reaction equation

HRID 2238408 reaction equation
Br[C:2]1[C:11]2[C:6](=[CH:7][C:8]([S:12]([CH3:15])(=[O:14])=[O:13])=[CH:9][CH:10]=2)[CH:5]=[CH:4][C:3]=1[N:16]([CH2:24][CH:25]=[CH:26][Cl:27])[C:17](=[O:23])[O:18][C:19]([CH3:22])([CH3:21])[CH3:20].CCCC[SnH](CCCC)CCCC.CC(N=NC(C#N)(C)C)(C#N)C>C1C=CC=CC=1>[Cl:27][CH2:26][CH:25]1[C:2]2[C:11]3[CH:10]=[CH:9][C:8]([S:12]([CH3:15])(=[O:14])=[O:13])=[CH:7][C:6]=3[CH:5]=[CH:4][C:3]=2[N:16]([C:17]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:23])[CH2:24]1

Participants

5

Reactant 3

HCID 5948TributylstannaneHCID 6547AzobisisobutyronitrileHCID 75066176HCID 75066176, compound

Product 1

HCID 44550374HCID 44550374, compoundYield 79%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

A mixture of 163 (5.38 g, 11.33 mmol), Bu3SnH (3.05 mL, 11.34 mmol) and AIBN (0.25 g, 1.5 mmol) in dry benzene (80 mL) under N2 was stirred at reflux for 2 h, then concentrated under reduced pressure. The residue was dissolved in CH2Cl2 and the solution was diluted with excess hexane and refrigerated. The precipitated semisolid was purified by chromatography on silica gel, eluting with CH2Cl2/EtOAc (19:1), to give tert-butyl 1-(chloromethyl)-7-(methylsulfonyl)-1,2-dihydro-3H-benzo[e]indole 3-carboxylate (164) (3.53 g, 79%) as a white solid: mp (iPr2O) 125-126° C.; 1H NMR [(CD3)2SO] δ 8.54 (d, J=1.8 Hz, 1H), 8.25-8.05 (m, 3H), 7.91 (dd, J=8.9, 1.9 Hz, 1H), 4.36-4.27 (m, 1H), 4.23 (t, f=10.5 Hz, 1H), 4.10 (dd, J=11.4, 2.9 Hz, 1H), 4.05 (dd, J=11.1, 3:2 Hz, 1H), 3.94 (dd, J=11.1, 6.7 Hz, 1H, 3.21 (after D2O exchange, s, 3H, 1.56 (s, 9H). Anal. (C19H22ClNO4S) C, H, N.

Workup

  1. temperatureat reflux for 2 h
  2. concentrationconcentrated under reduced pressure
  3. dissolutionThe residue was dissolved in CH2Cl2
  4. additionthe solution was diluted with excess hexane
  5. customThe precipitated semisolid was purified by chromatography on silica gel
  6. washeluting with CH2Cl2/EtOAc (19:1)

Sources & evidence

ORD record
ord-b97613abe35e4926a597676db2bacec8
Source dataset
uspto-grants-2010_05
Patent number
US07718688B2

Reaction notes

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