New Synthetic Methods Based on Titanacyclopropanes

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In this project funded by the Chemical Synthesis Program of the Chemistry Division, Professor Jin K. Cha of the Department of Chemistry at Wayne State University will explore synthetic applications of the low valent titanium-mediated cyclopropanation of esters and related cross-coupling reactions. By building on the original discovery by Kulinkovich, Professor Cha's group developed the olefin exchange-mediated variant to broaden the scope of the Kulinkovich cyclopropanation and pave the way for mechanistically related cross-coupling reactions. The specific goals include mechanistic studies of the key cyclopropananation reaction; low-valent titanium-mediated alkylation and cross-coupling reactions of allylic and homoallylic alcohols; and ring opening of cyclopropanols with a range of electrophiles in C-C bond forming reactions. Included are transition metal-catalyzed ring opening reactions. These reactions represent new uses of the Kulinkovich reagent with a broad scope and the well-defined stereochemical outcome. Particular emphasis will be placed at high efficiency and convergence, which is made possible by segment coupling.Professor Cha's approach lends itself to environmentally benign syntheses, which offer enabling technology to the pharmaceutical, chemical, agricultural industry, and materials science. Additionally, this project will provide training of coworkers, from undergraduate research participants to post-doctoral, including those from groups historically underrepresented in the physical sciences.