Polyol synthesis with beta-oxyanionic alkyllithium reagents: syntheses of aculeatins A, B, and D.
Synthesis of ketone aldol products using a non-aldol route was developed. The beta-phenylthio alcohols were prepared from optically pure oxiranes. Deprotonation and reductive lithiation generated the key intermediate, a beta-oxyanionic alkyllithium reagent. Addition to a Weinreb amide produced the beta-hydroxy ketone in >90% yield using only 1.5 equiv of the phenylthio alcohol. Stereoselective reduction of the ketone led to either the syn- or anti-1,3-diol. This simple, convergent sequence was used to prepare aculeatins A, B, and D from a common intermediate.
Malathong
Viengkham
V
Department of Chemistry, 1102 Natural Sciences II, University of California, Irvine, California 92697-2025, USA.
Rychnovsky
Scott D
SD
D000473:Alkanes / Q000138:chemical synthesis*; D002384:Catalysis; D003512:Cyclohexanones / Q000138:chemical synthesis*; D007202:Indicators and Reagents; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry; D018020:Lithium Compounds / Q000737:chemistry*; D004364:Pharmaceutical Preparations / Q000138:chemical synthesis / Q000737:chemistry; D013141:Spiro Compounds / Q000138:chemical synthesis*; D013237:Stereoisomerism
C436886:1,7-dioxa-dispiro(5.1.5.2)pentadeca-9,12-dien-11-one; D000473:Alkanes; D003512:Cyclohexanones; D007202:Indicators and Reagents; D007659:Ketones; D018020:Lithium Compounds; D004364:Pharmaceutical Preparations; D013141:Spiro Compounds; C476177:aculeatin A; C476176:aculeatin B
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