Rhodium-catalyzed atroposelective access to trisubstituted olefins<i>via</i>C–H bond olefination of diverse arenes

Zhu, Xiaomeng; Mi, Ruijie; Yin, Jie; Wang, Fen; Li, Xingwei

doi:10.1039/d3sc02714g

Cited by 12 publications

(3 citation statements)

References 85 publications

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Section: Asymmetric Alkyne Functionalization Strategymentioning

confidence: 99%

“…63 Very recently, the construction of axially chiral trisubstituted olefins was also achieved by the same group, which is more challenging in view of their much lower racemization barriers compared with tetrasubstituted alkenes. 64 Notably, pioneered by Tan 65 and Yan 66 in organocatalysis, hydrofunctionalization of sterically hindered alkynes is also a widely used methodology in the asymmetric synthesis of axially chiral styrenes. For transition metal catalysis, Li, Wang and coworkers applied this strategy in the construction of axially chiral olefins via palladium-catalyzed regio-and enantioselective hydrophosphination of bulky internal alkynes in 2022 (Scheme 22).…”

Section: Asymmetric Alkyne Functionalization Strategymentioning

confidence: 99%

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Transition-metal-catalyzed atroposelective synthesis of axially chiral styrenes

Qian,

Zhou,

Shi

2023

Chem. Commun.

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Section: Asymmetric Alkyne Functionalization Strategymentioning

confidence: 99%

Section: Asymmetric Alkyne Functionalization Strategymentioning

confidence: 99%

Transition-metal-catalyzed atroposelective synthesis of axially chiral styrenes

Qian,

Zhou,

Shi

2023

Chem. Commun.

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“…After the acceptance of this manuscript, a series of new papers on Rh-catalyzed asymmetric C−H functionalization reactions appeared (refs − ).…”

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confidence: 99%

Rhodium-Catalyzed Asymmetric C–H Functionalization Reactions

Liu,

Yin,

Zhao

et al. 2023

Chem. Rev.

102

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This review summarizes the advancements in rhodium-catalyzed asymmetric C–H functionalization reactions during the last two decades. Parallel to the rapidly developed palladium catalysis, rhodium catalysis has attracted extensive attention because of its unique reactivity and selectivity in asymmetric C–H functionalization reactions. In recent years, Rh-catalyzed asymmetric C–H functionalization reactions have been significantly developed in many respects, including catalyst design, reaction development, mechanistic investigation, and application in the synthesis of complex functional molecules. This review presents an explicit outline of catalysts and ligands, mechanism, the scope of coupling reagents, and applications.

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Rhodium(I)‐Catalyzed Asymmetric Hydroarylative Cyclization of 1,6‐Diynes to Access Atropisomerically Labile Chiral Dienes

Hu,

et al. 2023

Angewandte Chemie

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Axially chiral open‐chained olefins are an underexplored class of atropisomers, whose enantioselective synthesis represents a daunting challenge due to their relatively low racemization barrier. We herein report rhodium(I)‐catalyzed hydroarylative cyclization of 1,6‐diynes with three distinct classes of arenes, enabling highly enantioselective synthesis of a broad range of axially chiral 1,3‐dienes that are conformationally labile (delta G activation (rac) = 26.6‐28.0 kcal/mol). The coupling reactions in each category proceeded with excellent enantioselectivity, regioselectivity, and Z/E selectivity under mild reaction conditions. Computational studies of the coupling of quinoline N‐oxide system indicate that the reaction proceeds via initial oxidative cyclization of the 1,6‐diyne to give a rhodacyclic intermediate, followed by sigma‐bond metathesis between the arene C‐H bond and the Rh‐C(vinyl) bond, with subsequent C‐C reductive elimination being enantio‐determining and turnover‐limiting. The DFT‐established mechanism is consistent with the experimental studies. Significantly, the coupled products of quinoline N‐oxides undergo facile visible light‐induced intramolecular oxygen‐atom transfer, affording chiral epoxides with complete axial‐to‐central chirality transfer.

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Rhodium-catalyzed atroposelective access to trisubstituted olefinsviaC–H bond olefination of diverse arenes

Abstract: The atroposelective synthesis of axially chiral acyclic olefins remains a daunting challenge due to their relatively lower racemerization barriers, especially for trisubstituted ones. In this work, atroposelective C-H olefination has...

Cited by 12 publications

References 85 publications

Transition-metal-catalyzed atroposelective synthesis of axially chiral styrenes

Transition-metal-catalyzed atroposelective synthesis of axially chiral styrenes

Rhodium-Catalyzed Asymmetric C–H Functionalization Reactions

Rhodium(I)‐Catalyzed Asymmetric Hydroarylative Cyclization of 1,6‐Diynes to Access Atropisomerically Labile Chiral Dienes

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