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

Thesis/Dissertation · Tue Jan 01 00:00:00 EST 1985

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
• Resource Relation: Other Information: Thesis (Ph. D.)
• Country of Publication: United States
• Language: English

Related Subjects

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