Consolidation of the Oxidant‐Free Au(I)/Au(III) Catalysis Enabled by the Hemilabile Ligand Strategy

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(27)

Published: April 30, 2024

Abstract In this minireview we survey the challenges and strategies in gold redox catalysis. Gold's reluctance to oxidative addition reactions due its high potential limits applicability. Initial attempts overcome problem focused on use of sacrificial external oxidants stoichiometric amounts bring Au(I) compounds Au(III) reactive species. Recently, innovative approaches employing hemilabile ligands, which are capable coordinating stabilizing square‐planar intermediates, thus facilitating steps enabling oxidant‐free Notable examples include (P^N) bidendate MeDalphos ligand achieve various cross‐coupling via Au(I)/Au(III). Importantly, ligand‐enabled catalysis allows merging with π‐activation, such as oxy‐ aminoarylation alkenols alkenamines using organohalides, expanding gold‘s versatility C−C C‐heteroatom bond formations unprecedented cyclizations. Moreover, recent advancements enantioselective chiral ligands also surveyed. Strikingly, versatile bidentate (C^N) competitors have appeared recently, by designing scaffolds where phosphine groups substituted N‐heterocyclic or mesoionic carbenes. Overall, these highlight evolving landscape tremendous a broad scope transformations.

Language: Английский

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Dual gold/photoredox-catalyzed C(sp)–H arylation of terminal alkynes with diazonium salts

Chemical Science, Journal Year: 2015, Volume and Issue: 7(1), P. 89 - 93

Published: Oct. 8, 2015

The arylation of alkyl and aromatic terminal alkynes by a dual gold/photoredox catalytic system is described.

Language: Английский

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Visible light-mediated gold-catalysed carbon(sp²)–carbon(sp) cross-coupling

Chemical Science, Journal Year: 2015, Volume and Issue: 7(1), P. 85 - 88

Published: Nov. 10, 2015

A new method for the alkynylation of aryldiazonium salts with TMS-alkynes via dual gold and photoredox catalysis is described.

Language: Английский

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Selective Catalytic B–H Arylation of o-Carboranyl Aldehydes by a Transient Directing Strategy

Journal of the American Chemical Society, Journal Year: 2017, Volume and Issue: 139(41), P. 14511 - 14517

Published: Aug. 6, 2017

Carboranyl aldehydes are among the most useful synthons in derivatization of carboranes. However, compared to utilization carboranyl carboxylic acids selective B–H bond functionalizations, synthetic application is limited due weakly coordinating nature aldehyde group. Herein, direct arylation o-carboranyl has been developed via Pd-catalyzed cage functionalization. With help glycine generate a directing group (DG) situ, series B(4,5)-diarylated- and B(4)-monoarylated-o-carboranyl were obtained good excellent yields with high selectivity. A wide range functional groups tolerated. The arylated products could be readily removed or transformed into methanol. plausible catalytic cycle for was proposed based on control experiments stoichiometric reactions, including isolation key bicyclic palladium complex.

Language: Английский

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Ligand‐Assisted Gold‐Catalyzed Cross‐Coupling with Aryldiazonium Salts: Redox Gold Catalysis without an External Oxidant

Angewandte Chemie International Edition, Journal Year: 2015, Volume and Issue: 54(30), P. 8772 - 8776

Published: June 5, 2015

Gold-catalyzed C(sp)-C(sp(2)) and C(sp(2))-C(sp(2)) cross-coupling reactions are accomplished with aryldiazonium salts as the coupling partner. With assistance of bpy ligand, gold(I) species were oxidized to gold(III) by diazonium without any external oxidants. Monitoring reaction NMR ESI-MS provided strong evidence for nitrogen extrusion followed Au(III) reductive elimination key step.

Language: Английский

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