Ni‐Catalyzed Regioselective Hydroarylation of 1‐Aryl‐1,3‐Butadienes with Aryl Halides

Abstract

An efficient nickel-catalyzed regioselective hydroarylation of 1,3-dienes with aryl halides and a silane has been developed, affording a range of allylic arenes in good to excellent yields under mild conditions. This method exhibits broad substrate scope, and excellent functional group tolerance. Late-stage modification of complex architectures was demonstrated.

Nickel/Photoredox-Catalyzed Enantioselective Reductive Cross-Coupling between Vinyl Bromides and Benzyl Chlorides

“…[α] D 25 + 1.5 ( c 0.82, CHCl 3 ). The spectroscopic data for this product match the literature data …”

Nickel-catalyzed arylative substitution of homoallylic alcohols

“…Transition metal-catalyzed hydroarylations of 1,3-dienes are privileged synthetic methods to generate allylic arenes and allylic heteroarenes. 5–8 Traditionally, hydro(hetero)arylation of 1,3-dienes involves activation of an aryl C–H bond (Scheme 1a, top). 5,6 Alternatively, hydro(hetero)arylations of 1,3-dienes have been developed by employing alcohols or silanes as external hydride sources (Scheme 1a, bottom).…”

“…5,6 Alternatively, hydro(hetero)arylations of 1,3-dienes have been developed by employing alcohols or silanes as external hydride sources (Scheme 1a, bottom). 7,8 In the past decade, approaches to tandem transition metal-catalyzed hydro(hetero)arylation of 1,3-dienes generated in situ from homoallylic electrophiles have been reported. 9–11 Sigman and co-workers developed Pd-catalyzed arylative substitutions of primary and secondary homoallylic tosylates with arylboronic acids (Scheme 1b).…”

Nickel/SKP-Catalyzed Markovnikov Regio- and Enantioselective Hydroamination of Vinylarenes with Hydroxylamines

“…It is also notable that, in all cases reported so far for Ni-catalyzed asymmetric umpolung hydroamination, only N-donor ligands were known effective for stereochemical control. the development of Ni-catalysts for alkene hydrofunctionalization, 10 herein we report the first example of Ni catalyzed regioand enantioselective hydroamination of β-unsubstituted vinylarenes with hydroxylamines using SKP, 11 a chiral diphosphine ligand featured by adaptable structure and extraordinary large bite angle, 12 to furnish a broad range of chiral α-branched amines in high optical purities (Scheme 1d).…”

“…The elegant system worked well with three types of amination reagents (nitroarenes, hydroxylamines, and dioxazolones); unfortunately, there was only a single example for β-unsubstituted styrene, and the enantiocontrol was somewhat less satisfactory. It is also notable that, in all cases reported so far for Ni-catalyzed asymmetric umpolung hydroamination, only N -donor ligands were known effective for stereochemical control. , As an ongoing effort in the development of Ni-catalysts for alkene hydrofunctionalization, herein we report the first example of Ni catalyzed regio- and enantioselective hydroamination of β-unsubstituted vinylarenes with hydroxylamines using SKP, a chiral diphosphine ligand featured by adaptable structure and extraordinary large bite angle, to furnish a broad range of chiral α-branched amines in high optical purities (Scheme d).…”