Identifier: TDX:1962
Authors: Fedor Mikhailovich, Miloserdov
Abstract:
Activation and functionalization of unreactive carbon-halogen bonds is one of the primary tasks of modern chemistry. All three research projects fulfilled in the current Thesis deal with new reactions involving activation and cleavage of highly inert C-I, C-Br, C-Cl, and C-F bonds. Chapter 1 describes a new chemical transformation, Pd-catalyzed synthesis of aroyl azides from iodoarenes, CO, and NaN3. This catalytic process exhibits high efficiency (0.2% Pd) and excellent functional group tolerance. A detailed mechanistic study of the azidocarbonylation reaction has revealed two different reaction pathways operating in the presence of CO in excess and under CO-deficient conditions. Organometallic intermediates involved in the catalytic cycle have been isolated and fully characterized, including by X-ray diffraction. Chapter 2 reports a mechanistic study of the novel Ph-X (X = I, Br, Cl) activation with Ru(II) hydrido complexes under exceedingly mild conditions. Striking zeroth-order kinetics observed for the reaction of [(Ph3P)4Ru(H)2] with PhX (X = I, Br) originates from hidden autocatalysis that has been recognized and fully proven. Chapter 3 deals with C-F activation of highly inert fluoroform (CHF3), an industrially side-produced potent greenhouse gas, with alkali metal hydroxides and alkoxides. The reaction of MOR with CHF3 has been shown to furnish the corresponding orthoformates, exotic HC(OBu-t)3 included, in good to excellent yield. Results of the Thesis contribute to new methodology development, basic knowledge of reaction mechanisms, and potential ecological solutions.
Repositori URV