No abstract

The nickel-catalyzed direct carboxylation of alkenes with the cheap and abundantly available C1 building block carbon dioxide (CO2 ) in the presence of a base has been achieved. The one-pot reaction allows for the direct and selective synthesis of a wide range of α,β-unsaturated carboxylates (TON>100, TOF up to 6 h(-1) , TON=turnover number, TOF=turnover frequency). Thus, it is possible, in one step, to synthesize sodium acrylate from ethylene, CO2 , and a sodium salt. Acrylates are industrially important products, the synthesis of which has hitherto required multiple steps.

New Imido hydride complex 1 catalyzes a variety of silylation reactions that proceed via initial substrate activation but not silane addition.

Catalytic reduction of nitriles is considered as an attractive and atom‐economical route to a diversity of synthetically valuable primary amines. Compared to other methods, dihydroboration approach has been developed relatively recently but has already attracted the attention of many research groups due to reasonably mild reaction conditions, selectivity control and the access to N,N‐diborylamines, which emerged as powerful reagents for C−N bond forming reactions. Early developments in catalytic dihydroboration of nitriles implied precious metal catalysts along with harsh conditions and prolonged reaction times, whereas recent advances mostly rely on base and main group metal catalytic systems with significantly improved profiles. This minireview aims to provide an overview of advances and challenges of dihydroboration of nitriles with d‐, f‐ and main group metal catalysts. Mechanistic features of different catalytic systems, functional group tolerance and scope of the methods are also presented. The synthetic utility of N,N‐diborylamies, beyond simple protodeborylation, is discussed in the aspect of N‐arylation, imine and amide synthesis.