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

HRID 1922634Notes

Reaction equation

HRID 1922634 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.COC(N=NC(OC)=O)=O>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 351621Azodicarboxylic acid dimethyl esterHCID 59456526(R)-1-{(E,3S,3aS,7aR)-7-(bromomethylene)-octahydro-3a-methyl-1H-indene-3-yl}ethanol2×

Product 1

HCID 59456525(1Z,3aR,4E,7aS)-4-(bromomethylene)-1-ethylidene-octahydro-7a-methyl-1H-indeneYield 69.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Under a nitrogen atmosphere, a solution of (R)-1-{(E,3S,3aS,7aR)-7-(bromomethylene)-octahydro-3a-methyl-1H-indene-3-yl}ethanol (Compound 19: 20.8 mg, 0.07613 mmol) and triphenylphosphine (50 mg, 0.1903 mmol) in tetrahydrofuran (0.35 ml) was cooled in an ice bath, and azodicarboxylic acid dimethyl ester (2.7 M in toluene, 73.3 μl, 0.1979 mmol) was added dropwise thereto. The reaction mixture was stirred at the same temperature for 5 minutes and at room temperature for 40 hours, and then evaporated under reduced pressure. The obtained crude product was purified by flash column chromatography to obtain (1Z,3aR,4E,7aS)-4-(bromomethylene)-1-ethylidene-octahydro-7a-methyl-1H-indene (13.4 mg, 69.1%).

Workup

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

Sources & evidence

ORD record
ord-b0c4fecbdaeb4a3995a5975fc5b50914
Source dataset
uspto-grants-2012_05
Patent number
US08173824B2

Reaction notes

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