Carbon tetrabromide → (S)-t-butyl 2-(2,2-dibromovinyl)pyrrolidine-1-carboxylate

HRID 17172Notes

Reaction equation

HRID 17172 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:20]([Br:24])(Br)(Br)[Br:21].[C:25]([O:29][C:30]([N:32]1[CH2:36][CH2:35][CH2:34][CH:33]1[CH:37]=O)=[O:31])([CH3:28])([CH3:27])[CH3:26].C(=O)(O)[O-].[Na+]>ClCCl>[Br:21][C:20]([Br:24])=[CH:37][C@@H:33]1[CH2:34][CH2:35][CH2:36][N:32]1[C:30]([O:29][C:25]([CH3:26])([CH3:28])[CH3:27])=[O:31]

Participants

6

Reactant 4

HCID 11205Carbon tetrabromideHCID 11776TriphenylphosphineHCID 516892Sodium BicarbonateHCID 42278151-Boc-2-Formylpyrrolidine

Product 1

HCID 14730281(S)-t-butyl 2-(2,2-dibromovinyl)pyrrolidine-1-carboxylateYield 86%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A solution of triphenylphosphine (21.1 g, 80.3 mmol) and carbon tetrabromide (13.32 g, 40.16 mmol) in dichloromethane (300 mL) at 0° C. was treated with a solution of 2-formyl -pyrrolidine-1-carboxylic acid tert-butyl ester (4.0 g, 20.08 mmol) in dichloromethane (10 mL) dropwise via syringe. The solution was stirred for 1 hour at room temperature, poured into a saturated sodium bicarbonate solution and separated. The organic phase was dried (MgSO4), filtered and concentrated. The concentrate was purified by flash chromatography on silica gel using 0-1% methanol/dichloromethane to give 6.13 g (86% yield) of the desired product. 1H NMR (300 MHz, CHLOROFORM-D) δ ppm 1.47 (s, 9H), 1.81 (m, 3H), 2.16 (m, 1H), 3.39 (m, 2H), 4.37 (s, 1H), 6.38 (s, 1H).

Workup

  1. customseparated
  2. dry with materialThe organic phase was dried (MgSO4)
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customThe concentrate was purified by flash chromatography on silica gel using 0-1% methanol/dichloromethane

Sources & evidence

ORD record
ord-282782dd16794bb7bdd7cd11cc6d17f7
Source dataset
uspto-grants-2010_06
Patent number
US07737160B2

Reaction notes

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