Reductive 1,2-Arylation of Isatins

Abstract

We report an intermolecular Ni-catalyzed reductive coupling of aryl iodides and isatins to form 3-hydroxyoxindoles. In contrast to common metal-mediated methods, sec-butanol is used as a mild stoichiometric reductant resulting in benign waste products. This formal 1,2-addition reaction is facilitated by a 1,5-diaza-3,7diphosphacyclooctane (P 2 N 2 ) ligand. Two Ni(0)−P 2 N 2 species are prepared and found to be catalytically active, supporting a mechanistic hypothesis that this reaction proceeds by a modified carbonyl-Heck-type pathway.

A Non Expected Alternative Ni(0) Species in the Ni‐Catalytic Aldehyde and Alcohol Arylation Reactions Facilitated by a 1,5‐Diaza‐3,7‐diphosphacyclooctane Ligand

“…However, as stated above, this is not affordable thermodynamically. From intermediate II a second reaction can take place when R 1 I is inserted on this intermediate leading to the formation of III.1 which is also a Ni(0) species, in agreement with past work of Borys and Hevia, [52] Newman and coworkers, [39,53] and previously with palladium by Amatore and Jutand. [54] Then, the metal center is oxidized back to Ni(II) with the formation of III.2.…”

Visible-light-mediated C–F bond cleavage for the synthesis of polyfluorinated compounds

“…3 In recent years, a new strategy for the synthesis of different gem -difluoroolefins has been successfully established by using the β-F elimination of α-trifluoromethyl alkenes (Scheme 1a). 4–9 Under the conditions of transition-metal catalysis ( e.g. Ni, Fe, Cu, etc .…”