Reaction #3123

ord-8f870745fc5f496588a513ddc86e1f2b

Reaction equation

COC(=O)CCCCCSC1=C(O[SiH](C)C)[C@@H](C(C)(C)C)CC1=O
(4R)-tert-butyldimethylsiloxy-2-(5-methoxycarbonylpentylthio)-2-cyclopenten-1-one
CCCC[C@@H](C)C[C@@H](/C=C/I)O[Si](C)(C)C(C)(C)C
(1E,3S,5R)-1-iodo-3-(tert-butyldimethylsiloxy)-5-methyl-1-nonene
[Li][C](C)(C)C
tert-butyllithium
CC(C)C(=O)OC(=O)C(C)C
isobutyric anhydride
CCCCC#[C][Cu]
1-hexynylcopper
→
CCCC[C@@H](C)C[C@@H](/C=C/[C@@H]1C(SCCCCCC(=O)OC)=C(OC(=O)C(C)C)C[C@H]1O[Si](C)(C)C(C)(C)C)O[Si](C)(C)C(C)(C)C
methyl(11R,12S,13E,15S,17R)-9-isobutyryloxy-11,15-bis(tert-butyldimethylsiloxy)-17,20-dimethyl-7-thiaprosta-8,13-dienoate
Yield 65.0%

Reactants

COC(=O)CCCCCSC1=C(O[SiH](C)C)[C@@H](C(C)(C)C)CC1=O
(4R)-tert-butyldimethylsiloxy-2-(5-methoxycarbonylpentylthio)-2-cyclopenten-1-one
CCCC[C@@H](C)C[C@@H](/C=C/I)O[Si](C)(C)C(C)(C)C
(1E,3S,5R)-1-iodo-3-(tert-butyldimethylsiloxy)-5-methyl-1-nonene
[Li][C](C)(C)C
tert-butyllithium
CC(C)C(=O)OC(=O)C(C)C
isobutyric 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,5R)-1-iodo-3-(tert-butyldimethylsiloxy)-5-methyl-1-nonene (476 mg, 1.2 mmol), tert-butyllithium (1.54 mol/l, 1.56 ml, 2.4 mmol), 174 mg of 1-hexynylcopper, hexamethylphosphorous triamide (436 μl), (4R)-tert-butyldimethylsiloxy-2-(5-methoxycarbonylpentylthio)-2-cyclopenten-1-one (373 mg, 1 mmol), and isobutyric anhydride (448 μl), the same procedure was performed as in Example 1 to obtain methyl(11R,12S,13E,15S,17R)-9-isobutyryloxy-11,15-bis(tert-butyldimethylsiloxy)-17,20-dimethyl-7-thiaprosta-8,13-dienoate (466 mg, 65%).

Source

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