Ligand-Metal Cooperation Enables Net Ring-Opening C-C Activation / Difunctionalization of Cyclopropyl Ketones.

ABSTRACT: Reactions that cleave C-C bonds and enable functionalization at both carbon sites are powerful strategic tools in synthetic chemistry. Stereodefined cyclopropyl ketones have become readily available and would be an ideal source of 3-carbon fragments, but general approaches to net C-C activation / difunctionalization are unknown. Herein we demonstrate the cross-coupling of cyclopropyl ketones with organozinc reagents and chlorotrimethylsilane to form 1,3-difunctionalized, ring-opened products. A combination of experimental and theoretical studies rule out more established mechanisms and shed light on how cooperation between the redox-active terpyridine (tpy) ligand and the nickel atom enables the C-C bond activation step. The reduced (tpy^•-)Ni^I species activates the C-

SUBMITTER: Gilbert MM 

PROVIDER: S-EPMC11463996 | biostudies-literature | 2023 Sep

REPOSITORIES: biostudies-literature