While alkene hydroarylation methods have advanced rapidly over the past few years, Markovnikov-selective methods remain rare. Last year, we reported Ni-catalyzed hydroarylation of alkenyl carboxylic acid substrates with arylboronic acids, where the Markovnikov or anti-Markovnikov product could be accessed by changing the ligand environment around the metal center. In an Edge Article appearing online today in Chemical Science, we report a full account of our efforts to expand the substrate scope and elucidate the mechanism of the Markovnikov-selective (“ligand-free”) version of this method. Effective reaction conditions for alkenyl sulfonamides, ketones, and amides were identified, and detailed mechanistic studies suggested that the turnover-limiting and regiodetermining step is arylboronic acid transmetalation. Bravo to Zi-Qi, Omar, and Ruohan on this tour de force.
Click here for a link to the article in Chemical Science: https://pubs.rsc.org/en/content/articlelanding/2021/sc/d1sc03121j#!divAbstract
As a reminder, a pre-print of this article appeared back in May: https://chemrxiv.org/engage/chemrxiv/article-details/60c7592dbb8c1a05f33dcb81