Atropo‐Enantioselective Oxidation‐Enabled Iridium(III)‐Catalyzed C−H Arylations with Aryl Boronic Esters

Woźniak, Łukasz; Cramer, Nicolai

doi:10.1002/anie.202106403

Cited by 36 publications

(14 citation statements)

References 97 publications

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“…Apart from aryl bromides and diazo derivatives as effective substrates for the construction of axial chirality, Cramer et al recently applied boronic esters as nucleophilic coupling partners to achieve the CpIr(III)-catalyzed highly atropo-enantioselective C–H arylation of α-tetralone derivatives 85 . Pentan-3-yloxy ether-substituted chiral catalyst Ir-2 delivered oxime product 86 not only in higher yields but also with better enantioselectivity than other chiral iridium catalysts.…”

Section: Synthesis Of Atropisomers By Aryl–aryl Cross-couplingmentioning

confidence: 99%

Synthesis of Atropisomers by Transition-Metal-Catalyzed Asymmetric C–H Functionalization Reactions

et al. 2021

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Transition-metal-catalyzed enantioselective C−H functionalization has become a powerful strategy for the formation of C−C or C−X bonds, enabling the highly asymmetric synthesis of a wide range of enantioenriched compounds. Atropisomers are widely found in natural products and pharmaceutically relevant molecules, and have also found applications as privileged frameworks for chiral ligands and catalysts. Thus, research into asymmetric routes for the synthesis of atropisomers has garnered great interest in recent years. In this regard, transition-metal-catalyzed enantioselective C−H functionalization has emerged as an atom-economic and efficient strategy toward their synthesis. In this Perspective, the approaches for the synthesis of atropisomers by transition-metalcatalyzed asymmetric C−H functionalization reactions are summarized. The main focus here is on asymmetric catalysis via Pd, Rh, and Ir complexes, which have been the most frequently utilized catalysts among reported enantioselective C−H functionalization reactions. Finally, we discuss limitations on available protocols and give an outlook on possible future avenues of research.

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Section: Synthesis Of Atropisomers By Aryl–aryl Cross-couplingmentioning

confidence: 99%

Synthesis of Atropisomers by Transition-Metal-Catalyzed Asymmetric C–H Functionalization Reactions

et al. 2021

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“…Moreover, the resulted products could readily be reduced to the chiral P(III) compounds, which may find a potential application in asymmetric catalysis. In 2021, Woźniak and Cramer also achieved an enantioselective C–H arylation of tetralone derivatives with aryl boronic esters using a similar chiral Cp x Ir(III) complex …”

Section: Binaphthyl-derived Chiral Cyclopentadienyl Ligandsmentioning

confidence: 99%

Binaphthyl Scaffold: A Class of Versatile Structure in Asymmetric C–H Functionalization

et al. 2022

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Over the past decades, transition metal-catalyzed enantioselective C–H functionalization has emerged as a straightforward and powerful tool for the rapid access to chiral molecules. The enormous advances achieved in this emerging area largely rely on the development of chiral ligands that can enable both high levels of enantiocontrol and efficiency. Chiral ligands bearing binaphthyl scaffolds have been proven to be versatile in asymmetric C–H functionalization due to their availability, unique stereochemical features, and ease of fine-tuning steric and electronic properties. In this Review, we summarized the advance in the applications of chiral ligands on the basis of the binaphthyl scaffold in asymmetric C–H functionalization.

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“…Recently, the formation of axially chiral C–C or C–X bonds through asymmetric C–H activation catalyzed by transition metals has attracted extensive attention in atomic and step economics . The use of Pd, Rh, and Ir catalysis via asymmetric concerted metalation–deprotonation to form chiral M–C complexes has provided a variety of axially chiral products. Notably, chiral cyclopentadienyl (Cp X ) has been widely used in the Rh(III)-catalyzed asymmetric C–H activation reaction for synthesis of axially chiral compounds.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study of Rhodium-Catalyzed Dual C–H Activation to Synthesize C–N Axially Chiral N-Aryloxindoles: Origin of Axial Chirality

Liu

Zhang

et al. 2022

Organometallics

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The mechanism and origin of axial chirality of the Cp X Rh(III)-catalyzed asymmetric dual C−H bond activation reaction were investigated by density functional theory calculations. Theoretical studies indicated that this reaction occurred through C−H bond activation, acetylene insertion, second C−H bond activation, acetylene insertion into the Rh−vinyl bond, and protonation. The first alkyne migratory insertion was the rate-determining step and determined the high enantioselectivity in this reaction. Noncovalent interaction analysis was used to investigate the origin of axial chirality established by the spiro-Cp ligand. Furthermore, the substituent effects of the spiro-Cp ligand were calculated. The origin of axial chirality in this reaction was fully elucidated based on theoretical calculations.

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Atropo‐Enantioselective Oxidation‐Enabled Iridium(III)‐Catalyzed C−H Arylations with Aryl Boronic Esters

Cited by 36 publications

References 97 publications

Synthesis of Atropisomers by Transition-Metal-Catalyzed Asymmetric C–H Functionalization Reactions

Synthesis of Atropisomers by Transition-Metal-Catalyzed Asymmetric C–H Functionalization Reactions

Binaphthyl Scaffold: A Class of Versatile Structure in Asymmetric C–H Functionalization

Theoretical Study of Rhodium-Catalyzed Dual C–H Activation to Synthesize C–N Axially Chiral N-Aryloxindoles: Origin of Axial Chirality

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