USE OF RUTHENIUM COMPLEXES FOR FORMATION AND/OR HYDROGENATION OF AMIDES AND RELATED CARBOXYLIC ACID DERIVATIVES

摘要

A process for preparing amides by reacting a primary amine and a primary alcohol in the presence of a Ruthenium complex to generate the amide and molecular hydrogen. Primary amines are directly acylated by equimolar amounts of alcohols to produce amides and molecular hydrogen (the only byproduct) in high yields and high turnover numbers. Also disclosed are processes for hydrogenation of amides to alcohols and amines; hydrogenation of organic carbonates to alcohols; hydrogenation of carbamates or urea derivatives to alcohols and amines; amidation of esters; acylation of alcohols using esters; coupling of alcohols with water and a base to form carboxylic acids; dehydrogenation of beta-amino alcohols to form pyrazines and cyclic dipeptides; and dehydrogenation of secondary alcohols to ketones. These reactions are catalyzed by a Ruthenium complex which is based on a dearomatized PNN-type ligand of formula A1 or precursors thereof of formulae A2 or A3.

主权项

1. A process for (a) preparing a polypeptide or a cyclic dipeptide which comprises reacting a beta-aminoalcohol in the presence of a Ruthenium complex, or (b) preparing an amide, which comprises reacting a primary or secondary amine with an ester in the presence of a Ruthenium complex, wherein in each case the Ruthenium complex is represented by the structure of any one of formulae A1′, A2′ or A3′wherein
L1 is N(R)2; L2 is selected from the group consisting of nucleophilic carbene (CR2), P(R2), P(OR)2, N(R)2, imine, SR, SH, S(═O)R, heteroaryl wherein the heteroatom is selected from nitrogen and sulfur, As(R2), Sb(R)2 and an N-heterocyclic carbene represented by the structure: wherein each of R, R1, R2 and R3 are independently selected from the group consisting of alkyl, cycloalkyl, aryl, alkylaryl, heterocyclyl and heteroaryl; L3 is a mono-dentate two-electron donor selected from the group consisting of CO, P(R)3, P(OR)3, NO+, As(R)3, Sb(R)3, S(R)2, nitrile (RCN) and isonitrile (RNC) wherein R is as defined above; L4 is absent or is L3; Y and Z are each independently H or an anionic ligand selected from the group consisting of halogen, OCOR, OCOCF3, OSO2R, OSO2CF3, CN, OH, OR, N(R2), RS and SH; wherein R is as defined above; X represents zero, one, two or three substituents selected from the group consisting of alkyl, aryl, halogen, nitro, amide, ester, cyano, alkoxy, cycloalkyl, alkylaryl, heterocyclyl, heteroaryl, an inorganic support and a polymeric moiety; and anion represents a group bearing a single negative charge.