%0 Journal Article %A Tchawou, Augustin A. S. W. %A Raducan, Mihai %A Chen, Peter %D 2016 %T Mechanism-Based Design and Optimization of a Catalytic Electrophilic Cyclopropanation without Diazomethane %U https://acs.figshare.com/articles/journal_contribution/Mechanism-Based_Design_and_Optimization_of_a_Catalytic_Electrophilic_Cyclopropanation_without_Diazomethane/3520184 %R 10.1021/acs.organomet.6b00531.s001 %2 https://acs.figshare.com/ndownloader/files/5588981 %K spectroscopic studies %K cyclopropanation procedures %K electrophilic cyclopropanation %K boronic ester %K reaction kinetics point %K Catalytic Electrophilic Cyclopropanation %K Diazomethane Iodomethylboron compounds %K allylic alcohols %K Pd catalysts %X 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. %I ACS Publications