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TRANSITION METAL CATALYZED REDUCTIVE VINYLIDENE REACTIONSSourish Biswas (17272546) 24 October 2023 (has links)
<p dir="ltr">Vinylidenes are highly reactive intermediates that undergo a variety of chemical reactions. Our group has pioneered the in-situ generation of vinylidenes from bench stable 1,1-dichloroalkenes using transition metal catalysts and an exogenous reductant.</p><p dir="ltr">Herein, we demonstrate the intramolecular insertion of vinylidenes into Si–H bonds for the synthesis of unsaturated silacycles of different ring sizes. It is well known that the replacement of carbon for silicon are of significant interest to medicinal chemists as a strategy for improving the potency or pharmacokinetic properties of biologically active compounds. This method provides convenient access to trisubstituted vinyl silanes which are synthesized intermolecularly, including those that can be used as nucleophilic partners in Hiyama cross-coupling reactions. Finally, deuterium isotope labelling experiments reveal interesting mechanistic features of the reaction.</p><p dir="ltr">The second chapter of the thesis further highlights the reactivity of vinylidenes through utilizing a cobalt catalyst. Vinylidene complexes can be added into an alkyne intramolecularly followed by a cobalt to zinc transmetalation step. The resulting organozinc intermediate can be trapped with various electrophiles. Further, by altering the reaction condition, the cobaltacycle intermediate can be accessed using π systems to form different cycloadducts.</p>
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