An operationally convenient and general method for hydroboration of alkenes, aldehydes, and ketones employing Co(acac) 3 as a precatalyst is reported. The hydroboration of alkenes in the presence of HBpin, PPh 3 , and NaO t Bu affords good to excellent yields with high Markovnikov selectivity with up to 97:3 branched/linear selectivity. Moreover, Co(acac) 3 could be used effectively to hydroborate aldehydes and ketones in the absence of additives under mild reaction conditions. Inter-and intramolecular chemoselective reduction of the aldehyde group took place over the ketone functional group.

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Iron complexes [BIAN]Fe(I)(η6‐toluene) (M1) and [BIAN]FeCl2 (M2) (BIAN=bis(2,6‐diisopropylaniline)acenaphthene) were found to be viable catalysts for the regioselective hydroboration of alkynes and alkenes. The hydroboration of alkynes and alkenes in the presence of HBpin and an activator at 70 °C afforded linear vinyl and alkyl boronic esters, respectively. Selectivity up to 98% was observed for alkyl boronic esters and exclusive formation of trans product was observed for vinyl boronic esters.

Hydrosilylation of imines was achieved using a redox non-innocent Fe-BIAN catalyst and employing the inexpensive trialkoxysilane (EtO)3SiH.