Rhodium-Catalyzed Asymmetric C–H Functionalization Reactions

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(16), P. 10079 - 10134

Published: Aug. 1, 2023

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

Language: Английский

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Electrooxidative Rhodium(III)/Chiral Carboxylic Acid‐Catalyzed Enantioselective C−H Annulation of Sulfoximines with Alkynes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(15)

Published: Jan. 30, 2024

Abstract The combination of achiral Cp*Rh(III) with chiral carboxylic acids (CCAs) represents an efficient catalytic system in transition metal‐catalyzed enantioselective C−H activation. However, this hybrid catalysis is limited to redox‐neutral activation reactions and the adopt oxidative remains elusive pose a significant challenge. Herein, we describe development electrochemical Cp*Rh(III)‐catalyzed annulation sulfoximines alkynes enabled by acid (CCA) operationally friendly undivided cell at room temperature. A broad range enantioenriched 1,2‐benzothiazines are obtained high yields excellent enantioselectivities (up 99 % yield 98 : 2 er). practicality method demonstrated scale‐up reaction batch reactor external circulation. crucial intermediate isolated, characterized, transformed, providing rational support for Rh(III)/Rh(I) electrocatalytic cycle.

Language: Английский

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

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(15), P. 9359 - 9396

Published: July 18, 2022

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

Language: Английский

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Enantioselective synthesis of indenols via rhodium(III)–catalyzed C-H activation/annulation of ketones with alkynes

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 12, 2025

Language: Английский

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SCpRh(III)-Catalyzed Enantioselective Synthesis of Atropisomers by C2-Arylation of Indoles with 1-Diazonaphthoquinones

Organic Letters, Journal Year: 2022, Volume and Issue: 24(20), P. 3620 - 3625

Published: May 16, 2022

The Rh(III)-catalyzed highly enantioselective C2-arylation of indole derivatives with 1-diazonaphthoquinones is reported. In the presence 2.5 mol % SCpRh complex and 20 AgNO3, reactions indoles proceeded smoothly, affording a wide range C2-arylated atropisomers in good yields enantioselectivity (≤96% yield, ≤97% ee) under mild conditions. method displays broad substrate scope functional group tolerance.

Language: Английский

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Rhodium-Catalyzed Atroposelective C–H Arylation of (Hetero)Arenes Using Carbene Precursors as Arylating Reagents

Organic Letters, Journal Year: 2022, Volume and Issue: 24(17), P. 3189 - 3193

Published: April 25, 2022

Rhodium(III)-catalyzed C-H activation-based arylation of sterically hindered (hetero)arenes has been realized using diazo compounds and triazoles as arylating reagents for atroposelective synthesis two classes biaryls. The coupling 3-substituted indoles N-sulfonyltriazoles afforded with a C(2)-C chiral axis, while the 1-naphthylthioether ortho-quinone diazide binaphthyls. These systems proceeded under mild conditions via activation carbene insertion despite steric hindrance both arenes precursors.

Language: Английский

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Rh(III)-Catalyzed Atroposelective C–H Iodination of 1-Aryl Isoquinolines

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(8), P. 5127 - 5134

Published: March 30, 2023

The rhodium-catalyzed enantioselective C–H iodination of 1-aryl isoquinolines under mild conditions is disclosed. Direct with N-iodosuccinimide (NIS) catalyzed by chiral CpRh(III) complexes afforded a series axially biaryl iodides in excellent yields and enantioselectivity (up to 99% yield 97% ee). Furthermore, the atroposelective bromination chlorination reactions were also compatible. Notably, could be easily transformed QUINAP-type N,N-type ligands.

Language: Английский

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Synthesis of Hexamethyl-1,1′-spirobiindane-Based Chiral Spiro Cp Ligands and Their Application in Rhodium-Catalyzed Enantioselective Aryl C–H Addition to Nitroalkenes

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(13), P. 8838 - 8844

Published: June 20, 2023

Spiro cyclopentadienyl rhodium (SCpRh) complexes are powerful catalysts for promoting asymmetric C–H functionalization reactions. However, the application of chiral SCp ligands is limited due to tedious synthetic procedures and expensive starting materials. Herein, we have developed a series spiro (BCSCp) with 6–7 steps from commercially available cheap Bisphenol C. Their corresponding been prepared successfully applied in enantioselective aryl addition nitroalkenes, affording adducts up 88% yield 98% ee.

Language: Английский

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Advances in Exploring Cyclopentadienyl (Cp) Rhodium Catalysts Featuring Diastereotopic or Enantiotopic Cp Faces for Asymmetric C–H Activation

Synthesis, Journal Year: 2023, Volume and Issue: 55(09), P. 1309 - 1321

Published: Jan. 2, 2023

Abstract Chiral cyclopentadienyl rhodium (CpRh) complexes have emerged as a class of powerful catalysts for enantioselective C–H activation reactions. In terms Cp ligand development, the mainstream is to design chiral ligands with C 2 symmetry in order avoid problem face selectivity during their metalation rhodium. recent years, CpRh diastereotopic or enantiotopic faces were also revealed and successfully applied asymmetric activation. These advances are summarized this short review together perspectives future development. 1 Introduction Ligands Diastereotopic Faces 3 Enantiotopic 4 Conclusion Outlook

Language: Английский

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Asymmetric Intramolecular Amination Catalyzed with Cp*Ir-SPDO via Nitrene Transfer for Synthesis of Spiro-Quaternary Indolinone

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 18841 - 18847

Published: July 8, 2024

An asymmetric intramolecular spiro-amination to high steric hindering

Language: Английский

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