Borrowing hydrogen (BH) reactions are very useful for the sustainable synthesis of C‐C and C‐N bonds. They generally operate with transition metal‐based catalysts along with stoichiometric/catalytic amounts of added base. Here we report that two catalytic transformations, generally carried out with the BH methodology, i.e. N‐alkylation of amines with alcohols and β‐alkylation of secondary alcohols with primary alcohols, can be performed very effectively with just catalytic amounts of base under air without using any transition metal‐based catalyst. The mechanism is proposed to be based on air oxidation of the alcohol to aldehyde followed by condensation to an unsaturated intermediate which undergoes transfer hydrogenation with alcohol to the product.

Herein we report an efficient hydrosilylation strategy to selectively defunctionalize biomass-derived levulinic acid into value-added chemicals such as pentane-1,4-diol, pentan-2-ol, 2-MTHF and C 5 hydrocarbons by using cost-effective silanes and the commercially available catalyst B(C 6 F 5 ) 3 at room temperature. All reactions work well in chlorinated solvents but, as a greener alternative, most reactions can be run in toluene or solvent-less.