Ni-Catalyzed Regioselective 1,2-Dicarbofunctionalization of Olefins by Intercepting Heck Intermediates as Imine-Stabilized Transient Metallacycles

• Published in: Journal of the American Chemical Society Vol. 139; no. 31; pp. 10653 - 10656
• Main Authors: Shrestha, Bijay, Basnet, Prakash, Dhungana, Roshan K, KC, Shekhar, Thapa, Surendra, Sears, Jeremiah M, Giri, Ramesh
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 09.08.2017; Amer Chemical Soc; American Chemical Society (ACS)
• Subjects: alkenes; Chemistry; Chemistry, Multidisciplinary; imines; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; organic halogen compounds; Physical Sciences; regioselectivity; Science & Technology; 3-COMPONENT COUPLING REACTION; CARBON-MONOXIDE; RADICAL CYCLIZATION; QUATERNARY STEREOCENTERS; STEREOSELECTIVE-SYNTHESIS; UNACTIVATED OLEFINS; TERMINAL ALKENES; ARYLBORONIC ACIDS; ALKYL-HALIDES; CARBOXYLIC-ACIDS
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/jacs.7b06340

We disclose a strategy for Ni-catalyzed dicarbofunctionalization of olefins in styrenes by intercepting Heck C­(sp3)–NiX intermediates with arylzinc reagents. This approach utilizes a readily removable imine as a coordinating group that plays a dual role of intercepting oxidative addition species derived from aryl halides and triflates to promote Heck carbometalation and stabilizing the Heck C­(sp3)–NiX intermediates as transient metallacycles to suppress β-hydride elimination and facilitate transmetalation/reductive elimination steps. This method affords diversely substituted 1,1,2-triarylethyl products that occur as structural motifs in various natural products.