Ni-Catalyzed Regioselective β,δ-Diarylation of Unactivated Olefins in Ketimines via Ligand-Enabled Contraction of Transient Nickellacycles: Rapid Access to Remotely Diarylated Ketones

• Published in: Journal of the American Chemical Society Vol. 140; no. 25; pp. 7782 - 7786
• Main Authors: Basnet, Prakash, Dhungana, Roshan K, Thapa, Surendra, Shrestha, Bijay, KC, Shekhar, Sears, Jeremiah M, Giri, Ramesh
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 27.06.2018; Amer Chemical Soc
• Subjects: alkenes; Chemistry; Chemistry, Multidisciplinary; ketimines; ketones; moieties; organic halogen compounds; Physical Sciences; protons; regioselectivity; Science & Technology; ALKENYL CARBONYL-COMPOUNDS; ARYL BORONIC ACIDS; 3-COMPONENT COUPLING REACTION; RADICAL CYCLIZATION; HECK REACTIONS; BOND ACTIVATION; ALKYL BROMIDES; QUATERNARY CENTERS; TERMINAL ALKENES; INTERMOLECULAR CYANOTRIFLUOROMETHYLATION
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/jacs.8b03163

We disclose a [(PhO)3P]/NiBr2-catalyzed regioselective β,δ-diarylation of unactivated olefins in ketimines with aryl halides and arylzinc reagents. This diarylation proceeds at remote locations to the carbonyl group to afford, after simple H+ workup, diversely substituted β,δ-diarylketones that are otherwise difficult to access readily with existing methods. Deuterium-labeling and crossover experiments indicate that diarylation proceeds by ligand-enabled contraction of transient nickellacycles.