Enantioselective formal hydration of alpha,beta-unsaturated imides by Al-catalyzed conjugate addition of oxime nucleophiles.
The (salen)Al-catalyzed asymmetric conjugate addition of salicylaldoxime to alpha,beta-unsaturated imides is the key step in an efficient and highly enantioselective two-step formal hydration of these electron-deficient olefins. This reaction constitutes the first example of an enantioselective conjugate addition of an oxygen-centered nucleophile to alpha,beta-unsaturated carboxylic acid derivatives. Application of this method to chiral, nonracemic substrates revealed a high level of catalyst-induced diastereoselectivity, underscoring its potential utility for polyketide natural product synthesis.
Vanderwal
Christopher D
CD
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138, USA.
Jacobsen
Eric N
EN
D000438:Alcohols / Q000138:chemical synthesis; D000473:Alkanes / Q000737:chemistry; D000535:Aluminum / Q000737:chemistry*; D002264:Carboxylic Acids / Q000138:chemical synthesis*; D002384:Catalysis; D007094:Imides / Q000737:chemistry*; D010091:Oximes / Q000737:chemistry*; D013237:Stereoisomerism
D000438:Alcohols; D000473:Alkanes; D002264:Carboxylic Acids; D007094:Imides; D010091:Oximes; D000535:Aluminum