Switching between Hydrogenation and Olefin Transposition Catalysis via Silencing NH Cooperativity in Mn(I) Pincer Complexes.

ABSTRACT: While Mn-catalyzed (de)hydrogenation of carbonyl derivatives has been well established, the reactivity of Mn hydrides with olefins remains very rare. Herein, we report a Mn(I) pincer complex that effectively promotes site-controlled transposition of olefins. This reactivity is shown to emerge once the N-H functionality within the Mn/NH bifunctional complex is suppressed by alkylation. While detrimental for carbonyl (de)hydrogenation, such masking of the cooperative N-H functionality allows for the highly efficient conversion of a wide range of allylarenes to higher-value 1-propenybenzenes in near-quantitative yield with excellent stereoselectivities. The reactivity toward a single positional isomerization was also retained for long-chain alkenes, resulting in the highly regioselective form

SUBMITTER: Yang W 

PROVIDER: S-EPMC9442580 | biostudies-literature | 2022 Sep

REPOSITORIES: biostudies-literature