The anionic oxy-Cope rearrangement of bicyclo[2.2.2]octadienols serves as a key step for the construction of substituted bicyclo[5.3.1]undecenones and provides a novel entry to the AB ring system of the taxane diterpenes. The bicyclo[2.2.2]octadienols 11a-e underwent facile anionically-accelerated [3,3]-sigmatropic rearrangements to give bicyclo[5.3.1]undecenones 14a-e. Such reorganizations were also found to proceed in more highly substituted systems as evidenced by the transformations 27a-c→28a-c, 30→32, and 31→33. These bicyclo[5.3.1]undecenones were further functionalized by introducing a double bond conjugated to the carbonyl group (27a→40); moreover, oxygen functionality at C(13) could be introduced by allylic oxidation (28a→41 and 40→42). The enolates produced in situ by the anionic oxy-Cope rearrangement could be trapped by alkylating agents. These alkylations were highly stereoselective when the ketone enolate was trisubstituted as exemplified by the reactions 44→47 and 45→48. This entry to the taxane diterpenes allows access to the tricyclic ABC framework of the taxanes by annelation of the C ring onto an AB ring subunit as illustrated by the sequence 30→49→50.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Stereoselective construction of new carbon-carbon and carbon-heteroatom bonds constitutes one of the major challenges in modern synthetic organic chemistry. Consequently, numerous methods have been designed and developed to address this problem in both the context of relative and absolute stereochemical control. This review of synthetic approaches to Prelog-Djerassi lactone, which covers the period of 1963-1990, provides a useful overview of many of the useful tactics and devices that may be employed for the stereoselective assemblage of functionalized frameworks.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTStereoselective synthesis of (+)-Prelog-Djerassi lactone from furanoid intermediatesStephen F. Martin and Denise E. GuinnCite this: J. Org. Chem. 1987, 52, 25, 5588–5593Publication Date (Print):December 1, 1987Publication History Published online1 May 2002Published inissue 1 December 1987https://pubs.acs.org/doi/10.1021/jo00234a015https://doi.org/10.1021/jo00234a015research-articleACS PublicationsRequest reuse permissionsArticle Views1176Altmetric-Citations46LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

A facile, asymmetric synthesis of the methyl ester of Prelog-Djerassi lactone (3) has been completed in nine steps from furfuraldehyde (4).