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.1-3 Our research attempts to overcome this limitation by developing a strategy in which the functional group that drives the regioselectivity2-3 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 previously demonstrated by our group.4 Using experimental, mechanistic and computational studies, we show that a distal, 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.

Distal control of aryne capture regioselectivity by an in situ formed boronate

2019 Fall National Meeting

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