Synthesis of prostanoids; enantiomeric purity of alcohols by a /sup 31/P NMR technique

Thesis/Dissertation · Mon Dec 31 23:00:00 EST 1984

OSTI ID:6991609

Penning, T D

The enone, 2,2-diemthyl-3a..beta.., 6a..beta..-dihydro-4H-cyclopenta-1,3-dioxol-4-one, has been synthesized in six steps from cyclopentadiene, resolved using sulfoximine chemistry, and converted into (-)-prostaglandin E/sub 2/ methyl ester in three steps. Introduction of the optically pure omega side-chain using a conjugate addition of a stabilized organocopper reagent, followed by direct alkylation of the enolate with the ..cap alpha.. side-chain allylic iodide in the presence of hexamethylphosphoramide, afforded a trans, vicinally disubstituted cyclopentanone. Deprotection of the C-15 alcohol, followed by aluminum amalgam reduction of the C-10/oxygen bond, provided (-)-PGE/sub 2/ methyl ester in 47% overall yield from the enone. In an extension of previously described work, 2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-sulfide, prepared from l-ephedrine and thiophosphoryl chloride, was used to determine the enantiomeric excess of chiral alcohols in conjunction with /sup 31/P NMR. Chiral primary and secondary alcohols added quantitatively to the phospholidine to give diastereomers which could be analyzed by /sup 31/P NMR and HPLC. A number of other phosphorus heterocycles were also explored as potential chiral derivatizing reagents.

• Research Organization: Wayne State Univ., Detroit, MI (USA)
• OSTI ID: 6991609
• Country of Publication: United States
• Language: English

Related Subjects

550201* -- Biochemistry-- Tracer Techniques
59 BASIC BIOLOGICAL SCIENCES
ALCOHOLS
BIOSYNTHESIS
CHEMICAL REACTIONS
CHROMATOGRAPHY
DERIVATIZATION
ENANTIOMORPHS
ENOLS
HYDROXY COMPOUNDS
ISOTOPES
LIGHT NUCLEI
LIQUID COLUMN CHROMATOGRAPHY
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
NUCLEI
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
PHOSPHORUS 31
PHOSPHORUS ISOTOPES
PROSTAGLANDINS
RESONANCE
SEPARATION PROCESSES
STABLE ISOTOPES
STEREOCHEMISTRY
SYNTHESIS