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Comprehensive Mechanistic Analysis of Palladium- and Nickel-Catalyzed α,β-Dehydrogenation of Carbonyls via Organozinc Intermediates. | LitMetric

AI Article Synopsis

Article Abstract

Introducing degrees of unsaturation into small molecules is a central transformation in organic synthesis. A strategically useful category of this reaction type is the conversion of alkanes into alkenes for substrates with an adjacent electron-withdrawing group. An efficient strategy for this conversion has been deprotonation to form a stabilized organozinc intermediate that can be subjected to α,β-dehydrogenation through palladium or nickel catalysis. This general reactivity blueprint presents a window to uncover and understand the reactivity of Pd- and Ni-enolates. Within this context, it was determined that β-hydride elimination is slow and proceeds via concerted -elimination. One interesting finding is that β-hydride elimination can be preferred to a greater extent than C-C bond formation for Ni, more so than with Pd, which defies the generally assumed trends that β-hydride elimination is more facile with Pd than Ni. The discussion of these findings is informed by KIE experiments, DFT calculations, stoichiometric reactions, and rate studies. Additionally, this report details an in-depth analysis of a methodological manifold for practical dehydrogenation and should enable its application to challenges in organic synthesis.

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Source
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC11000628PMC
http://dx.doi.org/10.1021/acs.joc.3c02572DOI Listing

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