Mechanism-Based Design and Optimization of a Catalytic Electrophilic Cyclopropanation without Diazomethane Augustin A. S. W. Tchawou Mihai Raducan Peter Chen 10.1021/acs.organomet.6b00531.s001 https://acs.figshare.com/articles/journal_contribution/Mechanism-Based_Design_and_Optimization_of_a_Catalytic_Electrophilic_Cyclopropanation_without_Diazomethane/3520184 Iodomethylboron compounds, either the trifluoroborate or a boronic ester, cyclopropanate electron-rich olefins and unprotected allylic alcohols with Pd catalysts according to a novel, designed catalytic cycle. Proposed intermediates in a “diverted Heck” mechanism are observed by means of spectroscopic studies and by isolation and X-ray crystallographic characterization, which together with reaction kinetics point to a separation of rate-determining and product-determining steps, and a mechanism-based optimization of the yield, selectivity, and scope of the catalytic electrophilic cyclopropanation. The reaction with crystalline, air-stable, nonhygroscopic, and nontoxic reagents provides an alternative to Simmons–Smith-type reactions, as well as cyclopropanation procedures that require the use of diazomethane. 2016-08-04 18:50:13 spectroscopic studies cyclopropanation procedures electrophilic cyclopropanation boronic ester reaction kinetics point Catalytic Electrophilic Cyclopropanation Diazomethane Iodomethylboron compounds allylic alcohols Pd catalysts