New Synthetic Applications of Eco-friendly Organometallics of Magnesium, Zinc and Lanthanum in Organic Synthesis
Final Report Abstract
In this research project, we have improved the preparation of arylzinc halides (X = Br, I) by adding to commercial zinc powder catalytic amounts of InCl3 or In(acac)3 and LiCl. With these organozinc reagents, we have developed a new electrophilic thiolation leading to aryl(heteroaryl) thioethers. We have developed new magnesium reagents (sBu2Mg•2LiOR) for the performance of effective Br/Mgand Cl/Mg-exchanges in toluene. We have prepared new organolanthanum reagents (Bu2LaCl•4LiCl) for the preparation of condensed aromatic compounds. Also, we extended the preparation of solid organozinc pivalates to alkynylzinc pivalates with enhanced air and moisture stability. New Cr- and Cocatalyzed diastereoselective cross-couplings were developed as well as a cobalt-catalyzed acylation of S-pyridyl esters. A novel cobalt-catalyzed amination of organozinc reagents with various hydroxylamine benzoates has allowed the late stage electrophilic amination of various commercial drugs (fluoxetine, sertraline, paroxetine etc.).
