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Squaramide-catalyzed enantioselective Michael addition of masked acyl cyanides to substituted enones.

ABSTRACT: Masked acyl cyanide (MAC) reagents are shown to be effective umpolung synthons for enantioselective Michael addition to substituted enones. The reactions are catalyzed by chiral squaramides and afford adducts in high yields (90-99%) and with excellent enantioselectivities (85-98%). The addition products are unmasked to produce dicyanohydrins that, upon treatment with a variety of nucleophiles, provide γ-keto acids, esters, and amides. The use of this umpolung synthon has enabled, in enantiomerically enriched form, the first total synthesis of the prenylated phenol (+)-fornicin C.

SUBMITTER: Yang KS

PROVIDER: S-EPMC3968543 | biostudies-literature | 2013 Oct

REPOSITORIES: biostudies-literature

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Squaramide-catalyzed enantioselective Michael addition of masked acyl cyanides to substituted enones.

Yang Kin S KS Nibbs Antoinette E AE Türkmen Yunus E YE Rawal Viresh H VH

Journal of the American Chemical Society 20131017 43

Masked acyl cyanide (MAC) reagents are shown to be effective umpolung synthons for enantioselective Michael addition to substituted enones. The reactions are catalyzed by chiral squaramides and afford adducts in high yields (90-99%) and with excellent enantioselectivities (85-98%). The addition products are unmasked to produce dicyanohydrins that, upon treatment with a variety of nucleophiles, provide γ-keto acids, esters, and amides. The use of this umpolung synthon has enabled, in enantiomeric ...[more]

PMID: 24090310

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