Sadphos as Adaptive Ligands in Asymmetric Palladium Catalysis

Li, Wenbo; Zhang, Junliang

doi:10.1021/acs.accounts.3c00648

Acc. Chem. Res.

2024

DOI: 10.1021/acs.accounts.3c00648

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Sadphos as Adaptive Ligands in Asymmetric Palladium Catalysis

Wenbo Li,

Junliang Zhang

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2024

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Cited by 4 publications

(2 citation statements)

References 78 publications

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“…Remarkably, it has been discovered that chiral sulfinamides could act as an enantioselective bifunctional aminoarylation reagent toward the alkene in a stereoselective fashion . Furthermore, stereospecific transformations of chiral sulfinamides to other S(IV) and S(VI) compounds have also been demonstrated, not to mention that their utility in chiral ligands has been demonstrated in many catalytic asymmetric transformations …”

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confidence: 99%

Catalytic Asymmetric Synthesis of Sulfinamides via Cu-Catalyzed Asymmetric Addition of Aryl Boroxines to Sulfinylamines

Shi,

Yuan,

et al. 2024

J. Am. Chem. Soc.

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The application of sulfinamides has been witnessed in medicinal and agrochemistry with employment in asymmetric transformations. However, methods for their asymmetric catalytic synthesis have rarely been explored. Herein, the catalytic enantioselective addition of aryl boroxines to sulfinylamines via Cu catalyst and the newly developed Xuphos ligand were reported. A series of chiral aryl sulfinamides can be readily accessed in one step. This protocol enables the stereospecific transformation of sulfinamides to sulfonimidoyl fluorides, sulfonimidamides, and sulfonimidate esters. DFT calculations have revealed the reaction pathway, and the migratory insertion is the enantio-determining step. The noncovalent interaction between the oxygen atom of sulfinylamines and the C−H bonds in the ligand is crucial for enantioselectivity control.

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confidence: 99%

Catalytic Asymmetric Synthesis of Sulfinamides via Cu-Catalyzed Asymmetric Addition of Aryl Boroxines to Sulfinylamines

Shi,

Yuan,

et al. 2024

J. Am. Chem. Soc.

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“…The remaining ligands all performed with low yield, enantio- and regioselectivity. Inspired by the excellent performance of SadPhos ligands lately, we then screened our own developed SadPhos ligand kit to inspect the catalytic reactivity in this three-component reaction. Although almost all of the SadPhos ligands, such as Xiao-Phos , PC-Phos , Xu-Phos , TY-Phos , and Xiang-Phos could not deliver the desired product, Ming-Phos could show promising result.…”

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confidence: 99%

Pd-Catalyzed Enantioselective Three-Component Carboamination of 1,3-Cyclohexadiene

Wang,

Xu,

Wang

et al. 2024

J. Am. Chem. Soc.

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Asymmetric Pd-catalyzed three-component carboamination reactions of dienes to construct chiral cyclohexenylamines, which are of great importance in many fields of chemistry, have remained largely unexplored. Here, we demonstrate a highly enantio-and regioselective Pd/Ming-Phos-catalyzed carboamination reactions of 1,3-cyclohexadiene with readily available aryl iodides and anilines for facile access to diverse valuable chiral cyclohexenylamines. The process shows excellent functional group tolerance, easy scalability, and mild conditions. Moreover, mechanistic studies suggest that this reaction has a first-order dependence on the concentration of the palladium catalyst and aniline.

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Design and Application of New Pyridine-Derived Chiral Ligands in Asymmetric Catalysis

Zhang,

Ouyang,

Gao

et al. 2024

Acc. Chem. Res.

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Conspectus The innovation of chiral ligands has been crucial for the asymmetric synthesis of functional molecules, as demonstrated by several types of widely applied “privileged” ligands. In this context, chiral pyridine-derived ligands, by far some of the oldest and most widely utilized ligands in catalysis, have attracted considerable research interest in the past half-century. However, the development of broadly applicable chiral pyridine units (CPUs) has been plagued by several intertwining challenges, thus delaying advancements in many asymmetric reactions. This Account aims to summarize the recent progress in new CPU-containing ligands, focusing on a rationally designed, modular, and tunable CPU developed in our laboratory. A significant problem thwarting conventional designs is the paradox between broad reactivity and stereoselectivity; that is, while enhanced stereoselectivity may be achieved by introducing chiral elements close to the N atom, the concomitant increase in local steric hindrance often limits catalytic activity and scope. Our newly developed CPU features a rigid [6-5-3] fused-ring framework and a tunable spirocyclic ketal side wall. The well-defined three-dimensional structure minimizes local (inner layer) steric hindrance and tunes the peripheral environment (outer layer) by remote substituents, thus securing reactivity and stereoselectivity. Different chelating ligands were readily assembled using this chiral structural module, with applications in mechanistically diverse transition-metal-catalyzed reactions. Thus, a series of chiral 2,2′-bipyridine ligands were successfully employed in the development of a general, efficient, and highly enantioselective nickel-catalyzed intermolecular reductive addition, Ullmann coupling of ortho-chlorinated aryl aldehydes, and carboxylation of benzylic (pseudo)halides with CO2. Notably, these chiral 2,2′-bipyridine ligands exhibited superior catalytic activity in the reactions compared to common N-based ligands. In addition, highly enantioselective iridium-catalyzed C–H borylation was developed using a CPU-containing N,B-bidentate ligand. Furthermore, mechanistically challenging, additive-free, and broad-scope transfer hydrogenative direct asymmetric reductive amination was achieved using a half-sandwich iridium catalyst supported by a chiral N,C-bidentate ligand. The new ligands demonstrated excellent performance in securing high catalytic activity and stereoselectivity, which, when combined with experimental and computational mechanistic investigations, supported the “double-layer control” design concept. Considering the broad applications of pyridine-derived ligands, the research progress described herein should inspire the creation of novel chiral catalysts and drive the development of many catalytic asymmetric reactions.

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Sadphos as Adaptive Ligands in Asymmetric Palladium Catalysis

Cited by 4 publications

References 78 publications

Catalytic Asymmetric Synthesis of Sulfinamides via Cu-Catalyzed Asymmetric Addition of Aryl Boroxines to Sulfinylamines

Catalytic Asymmetric Synthesis of Sulfinamides via Cu-Catalyzed Asymmetric Addition of Aryl Boroxines to Sulfinylamines

Pd-Catalyzed Enantioselective Three-Component Carboamination of 1,3-Cyclohexadiene

Design and Application of New Pyridine-Derived Chiral Ligands in Asymmetric Catalysis

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