Coordination-assisted, transition-metal-catalyzed enantioselective desymmetric C–H functionalization

Yu, Xin; Zhang, Zhuo‐Zhuo; Niu, Jun‐Long; Shi, Bing‐Feng

doi:10.1039/d1qo01884a

Cited by 41 publications

(12 citation statements)

References 187 publications

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“…In particular, the direct C-H bond activation is one of the ideal and prominent ways to install functional groups at a desired site. [1][2][3][4] Apart from providing the necessary site-specific functionality, the direct C-H bond activation is beneficial due to its atom-efficient nature and late-stage functionalization ability, which could contribute to a sustainable approach. In this context, the ortho-C-H functionalization of aromatic compounds has often been well exemplified by the formation of proximal cyclometallation transition states.…”

Section: Introductionmentioning

confidence: 99%

Palladium catalyzed remote-meta-C–H functionalization of aniline scaffolds

Srinivas,

Satyanarayana

2024

Org. Chem. Front.

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Section: Introductionmentioning

confidence: 99%

Palladium catalyzed remote-meta-C–H functionalization of aniline scaffolds

Srinivas,

Satyanarayana

2024

Org. Chem. Front.

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“…Tremendous developments have been achieved in the past decades for transition-metal-catalyzed C–H functionalization reactions 1 – 8 . Recently, exploring 3d metal complexes in C–H functionalization has attracted considerable attention because of the earth-abundance and low toxicity of these metals compared with the 4d and 5d counterparts 9 – 12 .…”

Section: Introductionmentioning

confidence: 99%

Cobalt(III)-catalyzed asymmetric ring-opening of 7-oxabenzonorbornadienes via indole C–H functionalization

Zheng

Zhang

et al. 2023

Nat Commun

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Asymmetric ring-opening of 7-oxabenzonorbornadienes is achieved via Co-catalyzed indole C–H functionalization. The utilization of chiral Co-catalyst consisting of a binaphthyl-derived trisubstituted cyclopentadienyl ligand resulted in high yields (up to 99%) and excellent enantioselectivity (>99% ee) for the target products with tolerance for diverse functional groups. Opposite diastereoselectivities are obtained with chiral Co-catalyst or Cp*CoI2CO. Combined experimental and computational studies suggest β-oxygen elimination being the selectivity-determining step of the reaction. Meanwhile, the reactions of 7-azabenzonorbornadiene could also be executed in a diastereodivergent manner.

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“…However, despite extensive interest in this area, , the enantioselective [3 + 2] annulation of aldimines and alkenes has remained unexplored to date, probably due to the lack of suitable chiral catalysts that can not only promote the activation of an ortho -C(sp 2 )–H bond of an aldimine but can also show high activity and diastereo- and enantioselectivity for the alkene insertion and the subsequent addition of the resulting metal alkyl species to the imine unit. Regarding asymmetric C–H transformations, various chiral catalysts have been recently reported . However, catalyst-controlled enantioselective diastereodivergent transformation via C–H activation, which may provide an ideal route for the construction of different stereoisomers of a given chiral compound from the same set of starting materials, has remained a formidable challenge to date .…”

Section: Introductionmentioning

confidence: 99%

Enantioselective Synthesis of 1-Aminoindanes via [3 + 2] Annulation of Aldimines with Alkenes by Scandium-Catalyzed C–H Activation

et al. 2023

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Multisubstituted chiral 1-aminoindanes are important components in many pharmaceuticals and bioactive molecules. Therefore, the development of efficient and selective methods for the synthesis of chiral 1-aminoindanes is of great interest and importance. In principle, the asymmetric [3 + 2] annulation of aldimines with alkenes through C–H activation is the most atom-efficient and straightforward route for the construction of chiral 1-aminoindanes, but such a transformation has remained undeveloped to date probably due to the lack of suitable catalysts. Herein, we report for the first time the enantioselective [3 + 2] annulation of a wide range of aromatic aldimines and alkenes via ortho-C(sp2)–H activation by chiral half-sandwich scandium catalysts, which provides a straightforward route for the synthesis of multisubstituted chiral 1-aminoindanes. This protocol features 100% atom-efficiency, broad functional group compatibility, and high regio-, diastereo-, and enantioselectivity (up to >19:1 dr and 99:1 er). Remarkably, by fine-tuning the sterics of the chiral ligand around the catalyst metal center, the diastereodivergent asymmetric [3 + 2] annulation of aldimines and styrenes has been achieved with a high level of diastereo- and enantioselectivity, offering an efficient method for the synthesis of both the trans and cis diastereomers of a novel class of chiral 1-aminoindane derivatives containing two contiguous stereocenters from the same set of starting materials. Moreover, the asymmetric [3 + 2] annulation of aldimines with aliphatic α-olefins, norbornene, and 1,3-dienes has also been achieved.

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Coordination-assisted, transition-metal-catalyzed enantioselective desymmetric C–H functionalization

Abstract: Transition-metal-catalyzed asymmetric C-H functionalization has gradually emerged as a powerful tool for the creation of structural and chiral complexity in an atom- and step-economic fashion. The nature of this strategy...

Cited by 41 publications

References 187 publications

Palladium catalyzed remote-meta-C–H functionalization of aniline scaffolds

Palladium catalyzed remote-meta-C–H functionalization of aniline scaffolds

Cobalt(III)-catalyzed asymmetric ring-opening of 7-oxabenzonorbornadienes via indole C–H functionalization

Enantioselective Synthesis of 1-Aminoindanes via [3 + 2] Annulation of Aldimines with Alkenes by Scandium-Catalyzed C–H Activation

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