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The Biomimetic Synthesis and Final Structure Determination of (+)- and (−)-Centrolobine, Naturally Occurring Diarylheptanoid 2,6-cis-Disubstituted Tetrahydro-2H-pyrans

✍ Scribed by Frank Rogano; Peter Rüedi

Publisher: John Wiley and Sons
Year: 2010
Tongue: German
Weight: 444 KB
Volume: 93
Category: Article
ISSN: 0018-019X
DOI: 10.1002/hlca.201000096

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✦ Synopsis

Abstract

The enantiomerically pure title compounds were prepared by oxidative cyclization of their optically active diarylheptanoid precursors. The approach is considered as a biomimetic phenol oxidation via an intermediate quinone methide. The absolute configuration of the precursors is retained, and the transition state adopts the sterically most favorable diequatorial arrangement of the 2,6‐substituents to afford the __cis‐__configured natural products. The outcome unambiguously establishes the absolute configurations and the correlation with the chiroptical data. In addition, a problem of regioisomerism that had not been discussed before was solved, and the original assignment of the position of the MeO group in the natural centrolobines could be confirmed. As such the results are the experimental evidence for the corrections of long‐term inconsistencies we had postulated in an earlier review article.

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The Biomimetic Synthesis and First Characterization of the (+)- and (−)-Isocentrolobines, 2,6-cis- and 2,6-trans-Disubstituted Tetrahydro-2H-pyrans

✍ Frank Rogano; Georges Froidevaux; Peter Rüedi 📂 Article 📅 2010 🏛 John Wiley and Sons 🌐 German ⚖ 512 KB

## Abstract The four stereoisomers of the novel title compounds were prepared by oxidative cyclization of their enantiomerically pure diarylheptanoid precursors by means of the straightforward biomimetic approach presented in the preceding article. The isocentrolobines are the methoxy regioisomers