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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
- Source :
- Journal of the American Chemical Society. 122:9127-9133
- Publication Year :
- 2000
- Publisher :
- American Chemical Society (ACS), 2000.
-
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 thenow nondynamickinetic resolution of a structurally related, but centrochiral “aliphatic−aromatic” lactone, (rac)-10. Its highly efficient (krel > 300) enantiomer-differentiating Corey−Ba...
Details
- ISSN :
- 15205126 and 00027863
- Volume :
- 122
- Database :
- OpenAIRE
- Journal :
- Journal of the American Chemical Society
- Accession number :
- edsair.doi...........ffb390e849b5d3efcde2ba6569ee44cf