ABSTRACT
An α-diaminoboryl carbanion-mediated one-pot olefination directly converts an acetonitrile or the homologous nitrile into a series of α,ß-disubstituted acrylonitriles in a stereoselective manner. The protocol involves the formation of an α-substituted α-diaminoboryl acetonitrile and subsequent olefination with an aldehyde. The use of an aryl or conjugated aldehyde preferentially leads to a (Z)-acrylonitrile, while an aliphatic aldehyde gave an (E)-isomer as a major product. Two complementary approaches, a linear method and a divergent method, are developed.
ABSTRACT
A simple three-step single-pot procedure for Z-stereoselective synthesis of beta-monosubstituted acrylonitriles has been established. The reaction involves olefination of aldehydes with an in situ generated alpha-diaminoboryl carbanion species. Various aromatic and aliphatic aldehydes were smoothly converted into the corresponding (Z)-olefin products (up to 96:4 ratio) in good yields (80-98%).
Subject(s)
Acrylonitrile/chemistry , Acrylonitrile/chemical synthesis , Acetonitriles/chemistry , Acrylonitrile/analogs & derivatives , Aldehydes/chemistry , Molecular Structure , StereoisomerismABSTRACT
A simple, efficient, and environmentally-friendly heterogeneous Ru/C-catalyzed oxidation of secondary and primary alcohols without additives under an atmosphere of oxygen has been established.
Subject(s)
Alcohols/chemistry , Carbon/chemistry , Ruthenium/chemistry , Aldehydes/chemical synthesis , Aldehydes/chemistry , Catalysis , Ketones/chemical synthesis , Ketones/chemistry , Molecular Structure , Oxidation-Reduction , Oxygen/chemistryABSTRACT
A variety of aryl iodides were coupled with aromatic and aliphatic terminal alkynes to give the corresponding 1,2-disubstituted aromatic alkynes in good yields by using only 0.4 mol % of the heterogeneous 10 % Pd/C as the catalyst without a ligand, copper salt, or amine in an aqueous medium.
