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Heteroatom-Directed Acylation of Secondary Alcohols To Assign Absolute Configuration
Alexander S Burns1, Christopher C Ross1, Scott D Rychnovsky1
1Department of Chemistry, 1102 Natural Sciences II, University of California at Irvine , Irvine, California 92697, United States.
Abstract:
Birman's HBTM catalyst is effective for the enantioselective acylation and kinetic resolution of benzylic secondary alcohols. The enantioselective acylation has now been extended to secondary alcohols bearing electron-withdrawing groups such as halides and other heteroatoms. The level of selectivity is modest to good and is sufficient for determining configuration using the competing enantioselective conversion method. A mathematical analysis identifies conditions for achieving maximum differences in conversion and, consequently, assigning configuration with greater confidence. The new method is effective for halohydrins and secondary-tertiary 1,2-diols and was used to confirm the configuration of two inoterpene natural products.
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