MAIN GROUP CATALYSED C(sp3)-F BOND ACTIVATION AND FUNCTIONALISATION

AMIT KUMAR JAISWAL

Publication

MAIN GROUP CATALYSED C(sp3)-F BOND ACTIVATION AND FUNCTIONALISATION

AMIT KUMAR JAISWAL

Abstract

The prohibitive strength of the C(sp3)-F bond inspires researchers for the functionalisation of the aliphatic C-F bonds by harnessing the high fluorophilicity of main group Lewis acids along with concomitant formation of silicon fluoride bonds in order to render it in catalytic manner. This dissertation initially describes the aluminium catalysed Sonogashira coupling of aliphatic fluorides with silyl acetylides. Since it requires pre-installed TMS groups onto the incoming functional group, I have also developed a generic strategy for coupling aliphatic fluorides with a wider variety of unprotected nucleophiles by transforming the aliphatic fluoride into a meta-stable pseudohalide group. The pseudohalide is then readily displaced under mild conditions by H, C, O, N, S and P donor atom nucleophiles. Lastly, as psuedohalides are also often used as weakly coordinating anions (e.g. OTf-, NTf2-), I have developed a catalytic monoselective defluorination reaction, where the catalyst is regenerated via reaction with TMS psuedohalides.