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Insights into a Chemoselective Cobalt Catalyst for the Hydroboration of Alkenes and Nitriles

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journal contribution
posted on 26.04.2017, 20:13 by Abdulrahman D. Ibrahim, Steven W. Entsminger, Alison R. Fout
A chemoselective hydroboration protocol with terminal alkene substrates is reported using an electron-rich, low-valent cobalt pincer compound. The process is catalytic and leads to exclusive formation of anti-Markovnikov products, tolerating amino groups, esters, epoxides, ketones, and other functionalities. The protocol was successfully extended toward the hydroboration of nitriles, generating the corresponding amines in moderate to good yields. Labeling studies with deuterated pinacolborane gave insights into the mechanism, establishing the intermediacy of a cobalt hydride, as well as an insertion, β-hydride elimination, and alkene isomerization pathway. These insights provide a rationale for the observed regioselectivity and allow us to propose a catalytic mechanism.