1173722-19-4Relevant articles and documents
Cu(I)-catalyzed decarboxylative aldol-type and Mannich-type reactions for asymmetric construction of contiguous trisubstituted and quaternary stereocenters
Yin, Liang,Kanai, Motomu,Shibasaki, Masakatsu
scheme or table, p. 3497 - 3506 (2012/06/15)
The catalytic asymmetric decarboxylative aldol-type reaction between aldehydes and cyanocarboxylic acids and Mannich-type reaction between aldimines and cyanocarboxylic acids were developed. α,α,β-Trisubstituted- β-hydroxy nitriles bearing contiguous all-carbon quaternary and trisubstituted stereocenters were produced with moderate enantio- and diastereoselectivity in the presence of 10 mol % CuOAc-TANIAPHOS (or DTBM-SEGPHOS) complex in the aldol-type reaction. α,α,β- Trisubstituted-β-amino nitriles containing contiguous all-carbon quaternary and trisubstituted stereocenters were produced with moderate to high enantio- and diastereoselectivity using 5 mol % CuOAc-(R)-DTBM-SEGPHOS complex in the Mannich-type reaction. These reactions proceed through Cu(I)-catalyzed decarboxylative nucleophile generation, followed by the addition of the resulting chiral Cu-ketenimide to aldehydes or imines. Because the reactions proceed under very mild conditions at nearly neutral pH, the reactions are applicable to a wide range of substrate combinations, including both aromatic and aliphatic substrates. Finally, α,α,β-trisubstituted-β- amino nitriles were converted to β2,2,3-amino acid derivatives through simple acidic hydrolysis without any racemization and epimerization.
