Tributylstannane → Methyl 2-(benzyloxycarbonylamino)-3-(bicyclo[2.2.2]octan-1-yl)propanoate

HRID 451795Notes

Reaction equation

HRID 451795 reaction equation
[CH2:1]([O:8][C:9]([NH:11][C:12](=[CH2:17])[C:13]([O:15][CH3:16])=[O:14])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Br[C:19]12[CH2:26][CH2:25][CH:22]([CH2:23][CH2:24]1)[CH2:21][CH2:20]2.CC(N=NC(C#N)(C)C)(C#N)C.CCCC[SnH](CCCC)CCCC>C1C=CC=CC=1>[CH2:1]([O:8][C:9]([NH:11][CH:12]([CH2:17][C:19]12[CH2:26][CH2:25][CH:22]([CH2:23][CH2:24]1)[CH2:21][CH2:20]2)[C:13]([O:15][CH3:16])=[O:14])=[O:10])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 5948TributylstannaneHCID 6547AzobisisobutyronitrileHCID 1390601-Bromobicyclo(2.2.2)octaneHCID 3525700Z-Dehydro-Ala-OMe

Product 1

HCID 59201604Methyl 2-(benzyloxycarbonylamino)-3-(bicyclo[2.2.2]octan-1-yl)propanoateYield 15%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

methyl 2-(benzyloxycarbonylamino)acrylate (2.05 g, 0.0095 mol, 1 eq.), 1-bromobicyclo[2.2.2]octane (1.8 g, 0.0095 mol, 1 eq.) and AIBN (0.312 g, 0.0019 mol, 0.2 eq.) were dissolved in benzene (30 mL) and heated to reflux. Bu3SnH (5.53 g, 0.019 mol, 2 eq.) was then added. The resulting mixture was stirred at reflux for 14 hrs. The solvent was removed and the residue was purified via preparative TLC (EtOAc/Petroleum ether=1:9) to give methyl 2-(benzyloxycarbonylamino)-3-(bicyclo[2.2.2]octan-1-yl)propanoate (480 mg, 15%) as a foam. 1H NMR (CDCl3, 400 MHz) δ 7.35 (m, 5H), 5.13 (m, 2H), 4.42 (m, 1H), 3.73 (s, 3H), 1.8-1.1 (m, 15H), 1.28 (m, 1H).

Workup

  1. temperatureheated to reflux
  2. temperatureat reflux for 14 hrs
  3. customThe solvent was removed
  4. customthe residue was purified via preparative TLC (EtOAc/Petroleum ether=1:9)

Sources & evidence

ORD record
ord-5359ffdbdb834045b1930d37aa863b77
Source dataset
uspto-grants-2013_07
Patent number
US08487108B2

Reaction notes

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