(2-((3R,5R)-3,5-Bis((tert-butyldimethylsilyl)oxy)cyclohexylidene)ethyl)diphenylphosphine oxide → (4aS,8aS)-4-{(E)-2-[(3R,5R)-3,5-Bis-(tert-butyl-dimethyl-silanyloxy)-cyclohexylidene]-ethylidene}-8-((R)-1,5-dimethyl-5-trimethylsilanyloxy-hex-3-ynyl)-8a-methyl-1,2,3,4,4a,5,6,8a-octahydro-naphthalene

HRID 581610Notes

Reaction equation

HRID 581610 reaction equation
[C:1]([Si:5]([CH3:38])([CH3:37])[O:6][C@H:7]1[CH2:12][C@H:11]([O:13][Si:14]([C:17]([CH3:20])([CH3:19])[CH3:18])([CH3:16])[CH3:15])[CH2:10][C:9](=[CH:21][CH2:22]P(=O)(C2C=CC=CC=2)C2C=CC=CC=2)[CH2:8]1)([CH3:4])([CH3:3])[CH3:2].[Li]CCCC.[CH3:44][Si:45]([CH3:68])([CH3:67])[O:46][C:47]([CH3:66])([CH3:65])[C:48]#[C:49][CH2:50][C@H:51]([C:53]1[C@:54]2([CH3:64])[C@@H:59]([CH2:60][CH2:61][CH:62]=1)[C:58](=O)[CH2:57][CH2:56][CH2:55]2)[CH3:52]>C1COCC1>[C:1]([Si:5]([CH3:38])([CH3:37])[O:6][C@H:7]1[CH2:12][C@H:11]([O:13][Si:14]([C:17]([CH3:20])([CH3:19])[CH3:18])([CH3:15])[CH3:16])[CH2:10][C:9](=[CH:21]/[CH:22]=[C:58]2\[CH2:57][CH2:56][CH2:55][C@@:54]3([CH3:64])[C@H:59]\2[CH2:60][CH2:61][CH:62]=[C:53]3[C@H:51]([CH3:52])[CH2:50][C:49]#[C:48][C:47]([CH3:66])([O:46][Si:45]([CH3:44])([CH3:68])[CH3:67])[CH3:65])[CH2:8]1)([CH3:2])([CH3:4])[CH3:3]

Participants

5

Reactant 3

HCID 11146215(2-((3R,5R)-3,5-Bis((tert-butyldimethylsilyl)oxy)cyclohexylidene)ethyl)diphenylphosphine oxideHCID 67613097(4aS,8aR)-5-[(R)-5-Trimethylsilanyloxy-1,5-dimethyl-hex-3-ynyl]-4a-methyl-1,2,3,4,4a,7,8,8a-octahydro-naphthalen-1-oneHCID 178418339Butyllithium

Product 1

HCID 86754180(4aS,8aS)-4-{(E)-2-[(3R,5R)-3,5-Bis-(tert-butyl-dimethyl-silanyloxy)-cyclohexylidene]-ethylidene}-8-((R)-1,5-dimethyl-5-trimethylsilanyloxy-hex-3-ynyl)-8a-methyl-1,2,3,4,4a,5,6,8a-octahydro-naphthalene

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

511 mg (0.893 mmol) of carefully dried (3R,5R)-[2-[3,5-bis-(t-butyl-dimethyl-silanyloxy)-cyclohexylidene]-ethyl]-diphenyl-phosphine oxide (Tetrahedron Lett. 32, 7663 (1991)) was dissolved in 5 ml of abs. THF and treated at -78° with 0.65 ml of nBuLi (1.55M, hexane). 15 Minutes later, 179 mg (0.496 mmol) of (4aS,8aR)-5-[(R)-5-trimethylsilanyloxy-1,5-dimethyl-hex-3-ynyl]-4a-methyl-1,2,3,4,4a,7,8,8a-octahydro-naphthalen-1-one, dissolved in 0.5 ml of abs. THF, was added to the deep red solution and kept for 1 h at -78° and for 0.75 h at 0°. The reaction mixture was then poured onto crushed ice/KH2PO4, extracted twice with ether, washed with water and brine, dried over sodium sulfate, and the solvents carefully removed i.V. Flash chromatography (SiO2, hexane/AcOEt=9/1) afforded 108 mg of the title compound as colorless oil, besides 122 mg of recovered ketone in the more polar fractions.

Workup

  1. additionThe reaction mixture was then poured
  2. extractionextracted twice with ether
  3. washwashed with water and brine
  4. dry with materialdried over sodium sulfate

Sources & evidence

ORD record
ord-b9315813680f4cea9a8a8a5d830c4d77
Source dataset
uspto-grants-1999_07
Patent number
US05919986

Reaction notes

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