Control of Aryne Capture Regioselectivity via Fluoroboronate-induced Distortion

Sammanfattning: Arynes are valued as extremely versatile electrophilic intermediates. Control over the regioselectivity with which arynes react is typically achieved using comparatively simple and/or chemically inutile substituents close to the reactive triple bond. This poses a challenge for the broad acceptance of arynes as the basis of genuinely useful synthetic building blocks.The work in this thesis attempts to overcome this limitation by developing a strategy in which the boronate ester functional group that drives the regioselectivity of an aryne capture is installed at a remote location of the molecule and offers ample opportunity for further derivatisation. This has been achieved via a catalytic C-H borylation strategy.Using experimental, mechanistic and computational studies, we show that remote, boron-based functional group is temporarily activated in-situ into a form able to furnish unprecedented levels of aryne capture regioselectivity. After the aryne capture, the boronate may be used in myriad further manipulations to provide compounds that are difficult or impossible otherwise to synthesize.