An enantioselective central-axial-central chiral element transfer process leading to a concise synthesis of (+)-sterpurene: Intramolecular Diels-Alder reactions of vinylallene sulfoxides

Journal Article · Wed May 10 04:00:00 EDT 1989 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00192a033· OSTI ID:7121716

Gibbs, R A; Bartels, K; Lee, R W.K.; Okamura, W H ^[1]

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1. Univ. of California, Riverside (USA)

The intramolecular Diels-Alder (IMDA) reaction of vinylallene sulfoxide 19 as the diene component occurs in a rapid and stereoselective manner at room temperature to give tricyclic 20 in good yield. Sulfoxide 19 cyclizes {approximately} 140 times faster than the corresponding hydrocarbon 15a. It was also shown that gem-dimethyl substitution on the tether linking the vinylallene and vinyl group accelerates the rate of cyclization by only a factor of {approximately} 2.6. Treatment of enantiomerically enriched diene propargyl alcohol 6 with benzenesulfenyl chloride gave vinyallene sulfoxide 4 which cyclized in a highly enantio- and diastereoselective fashion to afford optically active tricyclic sulfoxide 5. Sulfoxide 5 was converted in two steps to the novel sesquiterpene fungal metabolite (+)-sterpurene, thus establishing its absolute configuration. By use of 2D NMR techniques, most of the proton and carbon signals in the {sup 1}H and {sup 13}C NMR spectra of sterpurene (8) and the precursor diene 33 were assigned.

• DOE Contract Number: FG03-86ER13535
• OSTI ID: 7121716
• Journal Information: Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 111:10; ISSN 0002-7863; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400000* -- Chemistry
400201 -- Chemical & Physicochemical Properties
CHEMICAL REACTIONS
DATA
DATA ANALYSIS
DIELS-ALDER REACTION
ENANTIOMORPHS
EXPERIMENTAL DATA
INFORMATION
MAGNETIC RESONANCE
MEASURING INSTRUMENTS
MEASURING METHODS
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
RESONANCE
SULFOXIDES