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

HRID 581615Notes

Reaction equation

HRID 581615 reaction equation
[Si:1]([O:8][C@H:9]1[CH2:14][C@H:13]([O:15][Si:16]([C:19]([CH3:22])([CH3:21])[CH3:20])([CH3:18])[CH3:17])[CH2:12][C:11](=[CH:23][CH2:24]P(=O)(C2C=CC=CC=2)C2C=CC=CC=2)[CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[Li]CCCC.[CH3:44][C@@H:45]([C@H:57]1[CH2:66][CH2:65][CH2:64][C@@H:63]2[C@:58]1([CH3:68])[CH2:59][CH2:60][CH2:61][C:62]2=O)[CH2:46][C:47]#[C:48][C:49]([CH3:56])([O:51][Si:52]([CH3:55])([CH3:54])[CH3:53])[CH3:50]>C1COCC1>[C:4]([Si:1]([CH3:2])([CH3:3])[O:8][C@H:9]1[CH2:14][C@H:13]([O:15][Si:16]([C:19]([CH3:22])([CH3:20])[CH3:21])([CH3:17])[CH3:18])[CH2:12][C:11](=[CH:23]/[CH:24]=[C:62]2\[CH2:61][CH2:60][CH2:59][C@@:58]3([CH3:68])[C@H:63]\2[CH2:64][CH2:65][CH2:66][C@@H:57]3[C@H:45]([CH3:44])[CH2:46][C:47]#[C:48][C:49]([CH3:56])([O:51][Si:52]([CH3:53])([CH3:54])[CH3:55])[CH3:50])[CH2:10]1)([CH3:5])([CH3:6])[CH3:7]

Participants

5

Reactant 3

HCID 11146215(2-((3R,5R)-3,5-Bis((tert-butyldimethylsilyl)oxy)cyclohexylidene)ethyl)diphenylphosphine oxideHCID 54264802(4aR,5R,8aR)-5-((R)-1,5-Dimethyl-5-trimethylsilanyloxy-hex-3-ynyl)-4a-methyl-octahydro-naphthalen-1-oneHCID 178418339Butyllithium

Product 1

HCID 21310063(4aR,5R,8aS)-1-{(E)-2-[(3R,5R)-3,5-Bis-(tert-butyl-dimethyl-silanyloxy)-cyclohexylidene]-ethylidene}-5-((R)-1,5-dimethyl-5-trimethylsilanyloxy-hex-3-ynyl)-4a-methyl-decahydro-naphthalene

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

590 mg (1.03 mmol) of carefully dried (3R,5R)-[2-[3,5-bis-(t-butyldimethylsilanyloxy)-cyclohexylidene]-ethyl]-diphenyl-phosphine oxide (Tetrahedron Lett. 32, 7663 (1991)) was dissolved in 5 ml of abs. THF and treated at -78° with 0.644 ml of nBuLi (1.6M, hexane). 15 Minutes later, 187 mg (5.15 mmol) of (4aR,5R,8aR)-5-((R)-1,5-dimethyl-5-trimethylsilanyloxy-hex-3-ynyl)-4a-methyl-octahydro-naphthalen-1-one, dissolved in 0.5 ml of abs. THF, was added to the deep red solution and kept for 0.5 h at -78° and for 0.5 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=95/5) afforded in the less polar fractions 129 mg of the title compound as colorless oil and in the more polar ones 67 mg of recovered ketone.

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-185b7e8577744174ab202d1fa29e5e0f
Source dataset
uspto-grants-1999_07
Patent number
US05919986

Reaction notes

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