Herein we describe the formation and use of silyl cobalt(III) dihydride complexes as powerful catalysts for the hydrosilylation of a variety of imines starting from a low-valent welldefined cobalt(I) complex. The reaction is efficient at low catalyst loadings with a diverse range of imines bearing various protecting groups, as well as aliphatic ketimines and quinoline. Kinetics, DFT calculations, NMR spectroscopic studies, deuteration experiments and X-ray diffraction analysis allowed us to propose a catalytic cycle based on silyl dihydrocobalt(III) complexes performing a hydrocobaltation.
We describe an efficient regio-and chemoselective dearomatization of N-heteroarenes using hydrido-cobalt catalysts. Reactions were performed under mild conditions on a wide range of N-heteroarenes leading exclusively to the silyl-1,2-dihydroheteroarene. Various quinolines and pyridines bearing electron-donating and electron-withdrawing substituents are compatible with this methodology. DFT calculations, NMR spectroscopic studies, and X-ray diffraction analysis underlined the importance of a second silane for the final step of the reaction.
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