Key points are not available for this paper at this time.
The synthetic potential of unsymmetrically substituted arynes is not yet fully realized due to regioselectivity issues. Although many models exist to predict the regioselectivity of arynes, these models do not hold for metal-mediated reactions. Previously, we reported a way to induce regioselectivity in a metal-catalyzed aryne annulation reaction by using bulky monodentate phosphine ligands. Reported herein is a mechanistic investigation into the operative catalytic cycle within this transformation. Additionally, the molecular parameters responsible for regioselectivity have been examined via LFERs and multivariate linear regression. This model shows the interdependence on both the steric and electronic properties of the aryne and the size of the phosphine ligand for regioselectivity.
Plasek et al. (Thu,) studied this question.