supporting data for "DIRHODIUM (II, II)- AND IRIDIUM (III)-CATALYZED INTRAMOLECULAR α-TRIFLUOROMETHYL-α-ALKYL CARBENE C(SP3)-H INSERTION REACTION"

Trifluoromethyl-bearing 5-membered rings are prevalent moieties in bioactive molecules, but modular approaches to these compounds by functionalization of robust C(sp3)–H bonds in a direct and selective manner are extremely challenging. Achieving high turnover numbers (TONs) with excellent stereo- and site-selectivity remains a pivotal objective in the field of organic chemistry. Currently, transition metal-catalyzed carbene transfer reactions have become predominant strategy for the construction of novel and complex structures in modern organic synthesis, because they could access new carbon-carbon and carbon-heteroatom bonds in one step, which makes them as major tools for organic chemists in the development of innovative methodology. Therefore, in this thesis, transition metal-catalyzed carbene insertion reactions into C(sp3)-H bonds are elaborately demonstrated to afford products containing saturated 5-membered ring with CF3 functional groups with excellent diastereo-, regio- and enantiocontrol and high TON. Kinetic isotope effect (KIE) studies, radical trapping experiment, low temperature HRMS (ESI+) analysis and UV-Vis spectroscopy as well as DFT calculations confirmed the involvement of metal carbene intermediates in the catalytic cycle.