The commercially availablea nd bench-stable Co(acac) 2 /dpephos system is employeda saprecatalyst for selective and efficient room temperature hydroboration of organicn itrilesw ith HBPin to produceaseries of N,N-diborylamines [RN(BPin) 2 ], which reacti ns itu with aldehydes to give aldimines. Formation of aldimines from N,Ndiborylamines does not require ad ehydrating agent, is applicable to aw ide range of N,N-diborylamine and aldehyde substrates and is highly chemoselective, being unaffected by various common functional groups,s uch as alkenes, alkynes,s econdary amines, ketones,e sters, amides, carboxylic acids, pyridines, nitriles, and nitro compounds. The overall transformation represents as ynthetically valuable approacht oa ldimines from nitrilesa nd can be performed in as equential one-pot manner,t olerating ester, lactone, carboxamide and unactivateda lkene functionalities.

The commercially available and bench‐stable Co(acac)2 ligated with bis[(2‐diphenylphosphino)phenyl] ether (dpephos) was employed for selective room temperature hydroboration of nitro compounds with HBPin (TOF up to 4615 h−1), tolerating halide, hydroxy, amino, ether, ester, lactone, amide and heteroaromatic functionalities. These reactions offered a direct access to a variety of N‐borylamines RN(H)BPin, which were in situ treated with aldehydes and carboxylic acids to produce a series of aldimines and secondary carboxamides without the need for dehydrating and/or coupling reagents. Combination of these transformations in a sequential one‐pot manner allowed for direct and selective synthesis of aldimines and secondary carboxamides from readily available and inexpensive nitro compounds.

Hydroboration of isocyanates with HBPin was demonstrated using both catalytic and catalyst-free approaches. In arene solvents, reactions employed the commercially available and bench-stable Co(acac)2/dpephos (dpephos = bis[(2-diphenylphosphino)phenyl] ether) pre-catalyst and...