C-Lithiation/Alkylation of Trimethylamine Cyanoborane

C-lithiation of trimethylamine cyanoborane readily occurs with 1.5 equiv of s-BuLi. The C-lithiated complex 1 reacts with various electrophiles such as alkyl iodides, aldehydes, ketones, allyl bromide, and bromotrimethylsilane to give the corresponding products 2−14, in excellent conversion and in good yields. This is the first example of C-lithiation/alkylation of an amine cyanoborane and allows the preparation of amine cyanoboranes not readily available before.