Reaction #3127

ord-76d32aafd0e142d0832c397f95f52a05

Reaction equation

COC(=O)CCCCCSC1=C(O[SiH](C)C)[C@@H](C(C)(C)C)CC1=O
(4R)-tert-butyldimethylsiloxy-2-(5-methoxycarbonyl-pentylthio)-2-cyclopenten-1-one
CCCCC[C@@H](/C=C/I)O[Si](C)(C)C(C)(C)C
(1E,3S)-1-iodo-3-(tert-butyldimethylsiloxy)-1-octene
[Li][C](C)(C)C
tert-butyllithium
O=C(OC(=O)c1ccccc1)c1ccccc1
benzoic anhydride
CCCCC#[C][Cu]
1-hexynylcopper
→
CCCCC[C@@H](/C=C/[C@@H]1C(SCCCCCC(=O)OC)=C(OC(=O)c2ccccc2)C[C@H]1O[Si](C)(C)C(C)(C)C)O[Si](C)(C)C(C)(C)C
methyl(11R,12S,13E,15S)-9-benzoyloxy-11,15-bis(tert-butyldimethylsiloxy)-7-thiaprosta-8,13-dienoate
Yield 55.4%

Reactants

COC(=O)CCCCCSC1=C(O[SiH](C)C)[C@@H](C(C)(C)C)CC1=O
(4R)-tert-butyldimethylsiloxy-2-(5-methoxycarbonyl-pentylthio)-2-cyclopenten-1-one
CCCCC[C@@H](/C=C/I)O[Si](C)(C)C(C)(C)C
(1E,3S)-1-iodo-3-(tert-butyldimethylsiloxy)-1-octene
[Li][C](C)(C)C
tert-butyllithium
O=C(OC(=O)c1ccccc1)c1ccccc1
benzoic anhydride
CCCCC#[C][Cu]
1-hexynylcopper

Reagents

None

Solvents

CN(C)P(N(C)C)N(C)C
hexamethylphosphorous triamide

Conditions

Detailed conditions
See reaction.notes.procedure_details.

Procedure

Using as the materials and reagents (1E,3S)-1-iodo-3-(tert-butyldimethylsiloxy)-1-octene (442 mg, 1.2 mmol), tert-butyllithium (1.54 mol/l, 1.56 ml, 2.4 mmol), 1-hexynylcopper (174 mg), hexamethylphosphorous triamide (436 μl), (4R)-tert-butyldimethylsiloxy-2-(5-methoxycarbonyl-pentylthio)-2-cyclopenten-1-one (373 mg, 1.0 mmol), and benzoic anhydride (661 mg), the same procedure was performed as in Example 1 to obtain methyl(11R,12S,13E,15S)-9-benzoyloxy-11,15-bis(tert-butyldimethylsiloxy)-7-thiaprosta-8,13-dienoate (239 mg, 33%).

Source

DOI: 10.6084/m9.figshare.5104873.v1Patent: US05731452uspto-grants-1998_03