Open AccessSquaramide-Catalyzed Enantioselective Michael Addition of Masked Acyl Cyanides to Substituted Enones
Author(s) -
Kin S. Yang,
Antoinette E. Nibbs,
Yunus E. Türkmen,
Viresh H. Rawal
Publication year - 2013
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/ja409012q
Subject(s) - chemistry , synthon , squaramide , enantioselective synthesis , umpolung , nucleophile , michael reaction , reagent , catalysis , organic chemistry , organocatalysis , phenol , cyanide , adduct , combinatorial chemistry
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.