Theoretical and experimental understanding of the pull-push effect on the synthesis of organoboranes, sulfides and selenides

Identifier:  TDX:2339

Handle: https://hdl.handle.net/20.500.11797/TDX2339

Authors:  Sanz López, Xavier

Abstract:
In this doctoral thesis the reactivity of B-B, B-Se and B-S containing species has been evaluated when reacting to unsaturated species such as vinyl epoxides and carbonylic alkenes and alkynes. It has been observed that the B-B containing reagents require an activation by alkoxydes or others, whilst the B-Se and B-S species are able to react by themselves with substrates without the need of additives to introduce a S or Se moiety. Thanks to these reagents, the metal-free synthesis of organoboranes, organosulfides and organoselenides has been achieved, being thus an outstanding advance in respect to the previously reported metal catalyzed synthesis. Moreover, DFT studies have helped to understand and propose plausible mechanisms for the reactions, being also very useful in the justification and comprehension of the experimentally observed trends on reactivity.