Zinc Hydride Catalyzed Chemoselective Hydroboration of Isocyanates: Amide Bond Formation and C=O Bond Cleavage

Herein, a remarkable conjugated bis-guanidinate (CBG) supported zinc hydride, [{LZnH}(2); L={(ArHN)(ArN)-C=N-C=(NAr)(NHAr); Ar=2,6-Et-2-C6H3}] (I) catalyzed partial reduction of heteroallenes via hydroboration is reported. A large number of aryl and alkyl isocyanates, including electron-donating and withdrawing groups, undergo reduction to obtain selectively N-boryl formamide, bis(boryl) hemiaminal and N-boryl methyl amine products. The compound I effectively catalyzes the chemoselective reduction of various isocyanates, in which the construction of the amide bond occurs. Isocyanates undergo a deoxygenation hydroboration reaction, in which the C=O bond cleaves, leading to N-boryl methyl amines. Several functionalities such as nitro, cyano, halide, and alkene groups are well-tolerated. Furthermore, a series of kinetic, control experiments and structurally characterized intermediates suggest that the zinc hydride species are responsible for all reduction steps and breaking the C=O bond.

Automated summary

A new zinc hydride catalyzed partial reduction of heteroallenes via hydroboration, selectively obtaining N-boryl formamide from various isocyanates with different functional groups, indicating potential for chemoselective reduction reactions.