Gold-catalyzed alkenylation and arylation of phosphorothioates

Urvashi,; Mishra, Sampoorna; Patil, Nitin T.

doi:10.1039/d3sc04888h

“…Also in 2022, the group of Patil achieved the C(sp 2 )À S cross-coupling of aryl iodides with arylsulfonyl hydrazides (Scheme 8f), [8i] and in 2023, they reported the synthesis of a wide scope of aryl alkyl ethers from the coupling of aryl iodides with aliphatic alcohols (Scheme 8g), [8j] and the alkenylation and arylation of phosphorothioates (Scheme 8h). [27] Strikingly, Xu reported the C(sp 2 )À O coupling of (hetero)aryl iodides with primary and secondary alcohols, proceeding in both inter-and intramolecular ways. The reactions were catalyzed either by (MeDalphos)AuCl or (RuPhos)AuCl efficiently, being the first time that RuPhos ligand was applied to gold-catalyzed cross-couplings (Scheme 8i).…”

Section: Hemilabile (P^n) Ligandsmentioning

confidence: 99%

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

Font,

Valdés,

Ribas

2024

Angewandte Chemie

1

0

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

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“…More specifically, they reported the first C−SCF 3 and C−SeCF 3 cross‐coupling reactions using (MeDalphos)AuCl as catalyst, AgSCF 3 and Me 4 NSeCF 3 as the nucleophilic SCF 3 and SeCF 3 sources, and aryl iodides, vinyl iodides, and alkynyl bromides as substrates. Also in 2022, the group of Patil achieved the C(sp 2 )−S cross‐coupling of aryl iodides with arylsulfonyl hydrazides (Scheme 8f), [8i] and in 2023, they reported the synthesis of a wide scope of aryl alkyl ethers from the coupling of aryl iodides with aliphatic alcohols (Scheme 8g), [8j] and the alkenylation and arylation of phosphorothioates (Scheme 8h) [27] . Strikingly, Xu reported the C(sp 2 )−O coupling of (hetero)aryl iodides with primary and secondary alcohols, proceeding in both inter‐ and intramolecular ways.…”

Section: Gold Redox Catalysismentioning

confidence: 99%

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

Font,

Valdés,

Ribas

2024

Angew Chem Int Ed

12

0

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

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“…The hemilabile MeDalPhos (P ∧ N) ligand ( 8 ) was introduced in the field by the same group three years later . The corresponding AuCl complex 13 was found to possess a remarkable reactivity that has been exploited over the past six years in the development of catalytic processes allowing C–C, C–N, C–O, and C–S bond formation by cross-coupling with aryl iodides. , Bower and Russel reported that the use of simple (N ∧ N) bidentate Bpy ligand (see 9 ) could also favor oxidative addition to Au(I), but the corresponding Au(III) complexes were found too fragile for catalysis . Very recently, interest has been focused toward the development of catalysts bearing (C ∧ N) ligands.…”

Section: Introductionmentioning

confidence: 99%

“…While it is now well established that the strategy of using bidentate ligands to enable oxidative addition of C–X bonds to Au(I) centers is effective, it remains that the number of available ligands allowing catalytic processes is extremely limited. (MeDalPhos)AuCl ( 13 ) remains the only general precatalyst and therefore the go-to when developing a new RedOx transformation . Surprisingly, very limited work has been done with respect to modifying the structure of MeDalPhos, which, in fact, is a repurposed ligand not initially designed for Au catalysis .…”

Section: Introductionmentioning

confidence: 99%

DFT-Enabled Development of Hemilabile (P^∧N) Ligands for Gold(I/III) RedOx Catalysis: Application to the Thiotosylation of Aryl Iodides

Muratov,

Zaripov,

Berezovski

et al. 2024

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Ligand-enabled oxidative addition of Csp 2 -X bonds to Au(I) centers has recently appeared as a valuable strategy for the development of catalytic RedOx processes. Several cross-coupling reactions that were previously considered difficult to achieve were reported lately, thus expanding the synthetic potential of gold(I) complexes beyond the traditional nucleophilic functionalization of π-systems. MeDalPhos has played an important role in this development and, despite several studies on alternative structures, remains, so far, the only general ligand for such process. We report herein the discovery and DFT-enabled structural optimization of a new family of hemilabile (P ∧ N) ligands that can promote the oxidative addition of aryl iodides to gold(I). These flexible ligands, which possess a common 2-methylamino heteroaromatic N-donor motif, are structurally and electronically tunable, beyond being easily accessible and affordable. The corresponding Au(I) complexes were shown to outperform the reactivity of (MeDalPhos)Au(I) in a series of alkoxy-and amidoarylations of alkenes. Their synthetic potential and comparatively higher reactivity were further highlighted in the thiotosylation of aryl iodides, a challenging unreported C−S cross-coupling reaction that could not be achieved under classical Pd(0/II) catalysis and that allows for general and divergent access to aryl sulfur derivatives.

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Gold-catalyzed alkenylation and arylation of phosphorothioates

Abstract: Reported herein is the ligand-enabled gold-catalyzed alkenylation and arylation of phosphorothioates using alkenyl and aryl iodides.

Cited by 25 publications

References 56 publications

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

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

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

DFT-Enabled Development of Hemilabile (P^∧N) Ligands for Gold(I/III) RedOx Catalysis: Application to the Thiotosylation of Aryl Iodides

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Gold-catalyzed alkenylation and arylation of phosphorothioates

Abstract: Reported herein is the ligand-enabled gold-catalyzed alkenylation and arylation of phosphorothioates using alkenyl and aryl iodides.

Cited by 25 publications

References 56 publications

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

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

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

DFT-Enabled Development of Hemilabile (P∧N) Ligands for Gold(I/III) RedOx Catalysis: Application to the Thiotosylation of Aryl Iodides

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DFT-Enabled Development of Hemilabile (P^∧N) Ligands for Gold(I/III) RedOx Catalysis: Application to the Thiotosylation of Aryl Iodides