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Nondynamic and dynamic kinetic resolution of lactones with stereogenic centers and axes: Stereoselective total synthesis of herbertenediol and mastigophorenes A and B

Bringmann, G., Pabst, T., Henschel, P., Kraus, J., Peters, K., Peters, E.M., Rycroft, D.S., and Connolly, J.D. (2000) Nondynamic and dynamic kinetic resolution of lactones with stereogenic centers and axes: Stereoselective total synthesis of herbertenediol and mastigophorenes A and B. Journal of the American Chemical Society, 122 (38). pp. 9127-9133. ISSN 0002-7863 (doi:10.1021/ja001455r)

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Publisher's URL: http://dx.doi.org/10.1021/ja001455r

Abstract

The stereoselective total synthesis of the sesquiterpene herbertenediol (3) and of its naturally occurring dimers, mastigophorenes A [(P)-1] and B [(M)-1], is. described. Following the "lactone concept",:the configuration at the biaryl axis was atropo-divergently induced to be P or, optionally, M, by stereocontrolled reductive ring cleavage (diastereomeric ratio up to 97:3) of the configurationally unstable joint biaryl lactone precursor 17 using the oxazaborolidine-borane system, through dynamic kinetic resolution. Mechanistic considerations of the lactone coupling suggested interference by a methoxy group next to the halogen substituent and led to an improvement of the coupling yield from 39 to 87% (to give the lactone 37). As a new, likewise highly efficient variant of the lactone method, we report for the first time, the-now nondynamic-kinetic resolution of a structurally related, but centrochiral "aliphatic-aromatic" lactone, (rac)-10. Its highly efficient (krel>300) enantiomer-differentiating Corey-Bakshi-Shibata reduction delivers the centrochiral building block (R,R)-10 in good chemical yield and with excellent stereochemical purity (enantiomeric excess >99.9%; enrichment of the starting matrial). The new synthesis of natural herbertenediol (3) confirms its absolute stereostructure as well as that of its dimers, (P)-1 and (M)-1.

Item Type:Article
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Connolly, Prof Joseph and Rycroft, Dr David
Authors: Bringmann, G., Pabst, T., Henschel, P., Kraus, J., Peters, K., Peters, E.M., Rycroft, D.S., and Connolly, J.D.
Subjects:Q Science > QD Chemistry
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Journal of the American Chemical Society
ISSN:0002-7863

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