Enantioselective syntheses of tremulenediol A and tremulenolide A.
[reaction: see text] An enantioselective entry to the skeleton of the tremulane sesquiterpenes is described. The approach features a series of efficient transition metal-catalyzed reactions commencing with an enantioselective rhodium(II)-catalyzed intramolecular cyclopropanation followed by a regioselective allylic alkylation and a diastereoselective rhodium(I)-catalyzed [5 + 2] cycloaddition. This strategy was applied to the first enantioselective syntheses of tremulenediol A and tremulenolide A.
Ashfeld
Brandon L
BL
Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, Texas 78712, USA.
Martin
Stephen F
SF
D000478:Alkylation; D002244:Carbon / Q000737:chemistry; D007783:Lactones / Q000737:chemistry; D008314:Malonates / Q000737:chemistry; D015394:Molecular Structure; D009930:Organic Chemicals / Q000138:chemical synthesis* / Q000737:chemistry; D012717:Sesquiterpenes / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
D007783:Lactones; D008314:Malonates; D009930:Organic Chemicals; D012717:Sesquiterpenes; C512231:tremulenediol A; C512232:tremulenolide A; D002244:Carbon; C030290:malonic acid