Rhodium-Catalyzed Asymmetric C–H Functionalization Reactions

Liu, Chen-Xu; Yin, Si-Yong; Zhao, Fangnuo; Yang, Hui; Feng, Zuolijun; Gu, Qing; You, Shu-Li

doi:10.1021/acs.chemrev.3c00149

Cited by 105 publications

(31 citation statements)

References 281 publications

(416 reference statements)

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“…Over the past few decades, substantial progress has been made in the field of (hetero)aromatic C–H activation. − Mechanisms such as electrophilic aromatic substitution (S E Ar), concerted metalation–deprotonation (CMD), σ-bond metathesis and Heck-type pathways have been firmly established as operative scenarios for the majority of C–H activation cases. , While the processes of C–H activation exhibit variations in different conditions, a consensus regarding the fundamental catalytic cycle modes for transition-metal-catalyzed oxidative Ar–H/Ar–H coupling reactions has gradually formed over the years. The elucidated mechanisms for oxidative Ar–H/Ar–H coupling reactions presented here are rooted in Pd(II) catalysis and categorized based on the presence or absence of a directing group (DG).…”

Section: Overview On Transition-metal-catalyzed Oxidative Ar–h/ar–h C...mentioning

confidence: 99%

Discovery of Organic Optoelectronic Materials Powered by Oxidative Ar–H/Ar–H Coupling

Yang,

Wu,

Bin

et al. 2024

J. Am. Chem. Soc.

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Efficient and streamlined synthetic methods that facilitate the rapid build-up of structurally diverse π-conjugated systems are of paramount importance in the quest for organic optoelectronic materials. Among these methods, transition-metalcatalyzed oxidative Ar−H/Ar−H coupling reactions between two (hetero)arenes have emerged as a concise and effective approach for generating a wide array of bi(hetero)aryl and fused heteroaryl structures. This innovative approach bypasses challenges associated with substrate pre-activation processes, thereby allowing for the creation of frameworks that were previously beyond reach using conventional Ar−X/Ar−M coupling reactions. These inherent advantages have ushered in new design patterns for organic optoelectronic molecules that deviate from traditional methods. This ground-breaking approach enables the transcendence of the limitations of repetitive material structures, ultimately leading to the discovery of novel high-performance materials. In this Perspective, we provide an overview of recent advances in the development of organic optoelectronic materials through the utilization of transition-metal-catalyzed oxidative Ar−H/Ar−H coupling reactions. We introduce several notable synthetic strategies in this domain, covering both directed and non-directed oxidative Ar−H/Ar−H coupling strategies, dual chelation-assisted strategy and directed ortho-C−H arylation/cyclization strategy. Additionally, we shed light on the role of oxidative Ar−H/Ar−H coupling reactions in the advancement of high-performance organic optoelectronic materials. Finally, we discuss the current limitations of existing protocols and offer insights into the future prospects for this field.

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Section: Overview On Transition-metal-catalyzed Oxidative Ar–h/ar–h C...mentioning

confidence: 99%

Discovery of Organic Optoelectronic Materials Powered by Oxidative Ar–H/Ar–H Coupling

Yang,

Wu,

Bin

et al. 2024

J. Am. Chem. Soc.

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“…Over the past decade, transition-metal-catalyzed enantioselective C–H functionalization reactions have contributed tremendously to the improvement of molecular complexity from readily available chemical feedstocks. − Notably, Rh(I)-catalyzed asymmetric C–H functionalization reactions have progressed rapidly. − In 2004, Bergman, Ellman, and co-workers made a breakthrough in Rh(I)-catalyzed intramolecular asymmetric C–H alkylation reaction using an imine as a directing group . Later, several elegant works for Rh(I)-catalyzed asymmetric C–H functionalization reactions have been demonstrated. − In 2016, Glorius and co-workers achieved remarkable progress in the combination of a rhodium(I) precatalyst with a chiral N-heterocyclic carbene (NHC) or monodentate phosphonite ligand enabled asymmetric C(sp 3 )–H arylation in good yields and enantioselectivity. , Our group recently explicated the mechanism of Rh(I)-catalyzed asymmetric C–H arylation, which first occurs by a directed C–H activation through a concerted metalation–deprotonation (CMD) pathway and the reductive elimination is the turnover-limiting step .…”

Section: Introductionmentioning

confidence: 99%

Enantioselective Rh(I)-Catalyzed C–H Arylation of Ferroceneformaldehydes

Liu,

Zhao,

et al. 2023

ACS Cent. Sci.

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As an important class of platform molecules, planar chiral ferrocene carbonyl compounds could be transformed into various functional groups offering facile synthesis of chiral ligands and catalysts. However, developing efficient and straightforward methods for accessing enantiopure planar chiral ferrocene carbonyl compounds, especially ferroceneformaldehydes, remains highly challenging. Herein, we report a rhodium(I)/phosphoramidite-catalyzed enantioselective C–H bond arylation of ferroceneformaldehydes. Readily available aryl halides such as aryl iodides, aryl bromides, and even aryl chlorides are suitable coupling partners in this transformation, leading to a series of planar chiral ferroceneformaldehydes in good yields and excellent enantioselectivity (up to 83% yield and >99% ee). The aldehyde group could be transformed into diverse functional groups smoothly, and enantiopure Ugi’s amine and PPFA analogues could be synthesized efficiently. The latter was found to be a highly efficient ligand in Pd-catalyzed asymmetric allylic alkylation reactions. Mechanistic experiments supported the formation of imine intermediates as the key step during the reaction.

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“…3 For instance, remarkable achievements have been made by pioneers including Miura, Glorius, Chang, Ellman, Rovis, and Li, as well as by other groups, with respect to Rh( iii )-catalyzed C–H activation reactions. 4…”

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confidence: 99%