Directed Markovnikov hydroarylation and hydroalkenylation of alkenes under nickel catalysis

• Published in: Chemical science (Cambridge) Vol. 12; no. 33; pp. 1138 - 1144
• Main Authors: Li, Zi-Qi, Apolinar, Omar, Deng, Ruohan, Engle, Keary M
• Format: Journal Article
• Language: English
• Published: CAMBRIDGE Royal Soc Chemistry 25.08.2021; Royal Society of Chemistry; The Royal Society of Chemistry
• Subjects: Alkenes; Catalysis; Chemistry; Chemistry, Multidisciplinary; Coordination; Functional groups; Nickel; Physical Sciences; Regioselectivity; Science & Technology; Substrates; Sulfonamides; FUNCTIONALIZATION; 1,2-DIARYLATION; PALLADIUM; 1,3-DIENES; ACIDS; ARYL HALIDES; OLEFINS; MECHANISMS; SELECTIVE HYDROARYLATION; UNACTIVATED ALKENES
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/d1sc03121j

We report a full account of our research on nickel-catalyzed Markovnikov-selective hydroarylation and hydroalkenylation of non-conjugated alkenes, which has yielded a toolkit of methods that proceed under mild conditions with alkenyl sulfonamide, ketone, and amide substrates. Regioselectivity is controlled through catalyst coordination to the native Lewis basic functional groups contained within these substrates. To maximize product yield, reaction conditions were fine-tuned for each substrate class, reflecting the different coordination properties of the directing functionality. Detailed kinetic and computational studies shed light on the mechanism of this family of transformations, pointing to transmetalation as the turnover-limiting step. Native Lewis basic functional groups enable the nickel-catalyzed Markovnikov-selective hydroarylation and hydroalkenylation of unactivated alkenes with organoboron reagents.