Triphenylphosphine → (1E,3aR,4E,7aS)-4-(bromomethylene)-1-ethylidene-octahydro-7a-methyl-1H-indene

HRID 1922635Notes

Reaction equation

HRID 1922635 reaction equation
[Br:1]/[CH:2]=[C:3]1\[CH2:4][CH2:5][CH2:6][C@@:7]2([CH3:15])[C@H:11]\1[CH2:10][CH2:9][C@@H:8]2[C@@H:12](O)[CH3:13].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(OC(N=NC(OCC)=O)=O)C>O1CCCC1>[Br:1]/[CH:2]=[C:3]1/[C@H:11]2[C@:7]([CH3:15])([CH2:6][CH2:5][CH2:4]/1)/[C:8](=[CH:12]/[CH3:13])/[CH2:9][CH2:10]2

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 59456539(S)-1-{(E,3S,3aS,7aR)-7-(bromomethylene)-octahydro-3a-methyl-1H-indene-3-yl}ethanol2×

Product 1

HCID 59456521(1E,3aR,4E,7aS)-4-(bromomethylene)-1-ethylidene-octahydro-7a-methyl-1H-indeneYield 44.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Under a nitrogen atmosphere, a solution of (S)-1-{(E,3S,3aS,7aR)-7-(bromomethylene)-octahydro-3a-methyl-1H-indene-3-yl}ethanol (Compound 18: 52.4 mg, 0.1918 mmol) and triphenylphosphine (126 mg, 0.4795 mmol) in tetrahydrofuran (0.3 ml) was cooled in an ice bath, and azodicarboxylic acid diethyl ester (2.2 M in toluene, 223.4 μl, 0.4915 mmol) was added dropwise thereto. The reaction mixture was stirred in the ice bath for 10 minutes and at room temperature for 21 hours, and then evaporated under reduced pressure. The obtained crude product was purified by flash column chromatography to obtain (1E,3aR,4E,7aS)-4-(bromomethylene)-1-ethylidene-octahydro-7a-methyl-1H-indene (21.8 mg, 44.6%).

Workup

  1. customevaporated under reduced pressure
  2. customThe obtained crude product
  3. customwas purified by flash column chromatography

Sources & evidence

ORD record
ord-45d9ab5d91d64b2ba5c527c086942bbe
Source dataset
uspto-grants-2012_05
Patent number
US08173824B2

Reaction notes

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