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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Cobalt‐Catalyzed Enantioselective C−H Carbonylation towards Chiral Isoindolinones

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(10)

Published: Jan. 11, 2024

Transition metal-catalyzed enantioselective C-H carbonylation with carbon monoxide, an essential and easily available C1 feedstock, remains challenging. Here, we disclosed unprecedented catalyzed by inexpensive readily cobalt(II) salt. The reactions proceed efficiently through desymmetrization, kinetic resolution, parallel affording a broad range of chiral isoindolinones in good yields excellent enantioselectivities (up to 92 % yield 99 ee). synthetic potential this method was demonstrated asymmetric synthesis biological active compounds, such as (S)-PD172938 (S)-Pazinaclone. resulting also serve ligands cobalt-catalyzed annulation alkynes construct phosphorus stereocenter.

Language: Английский

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Synthesis of Axially Chiral Biaryls through Cobalt(II)‐Catalyzed Atroposelective C−H Arylation

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(40)

Published: Aug. 16, 2023

Highly efficient synthesis of axially chiral biaryl amines through cobalt-catalyzed atroposelective C-H arylation using easily accessible cobalt(II) salt and salicyloxazoline ligand has been reported. This methodology provides a straightforward sustainable access to broad range enantioenriched biaryl-2-amines in good yields (up 99 %) with excellent enantioselectivities % ee). The synthetic utility the unprecedented method is highlighted by its scalability diverse transformations.

Language: Английский

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Copper/BINOL-Catalyzed Enantioselective C–H Functionalization toward Planar Chiral Ferrocenes Under Mild Conditions

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(6), P. 4030 - 4039

Published: Feb. 28, 2024

Copper-catalyzed enantioselective C–H activation proceeding through an inner-sphere mechanism remains a huge challenge. Herein, copper-catalyzed alkynylation with terminal alkynes assisted by 8-aminoquinoline using readily available (S)-BINOL as the chiral ligand was disclosed. The reaction proceeded under mild conditions catalytic amount of copper salt, providing range ferrocenes in good yields and enantioselectivities (0 °C, up to 77% yield 94% ee). alteration stoichiometric chemical oxidant renewable electricity is also feasible at ambient temperature, demonstrating robustness this copper/BINOL catalysis. Notably, first cupraelectrocatalyzed reaction. Gram-scale synthesis, versatile transformations, application resulting oxazoline–olefin asymmetric synthesis highlight utility protocols.

Language: Английский

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Pd(II)-Catalyzed Enantioselective C(sp³)–H Arylation toward P-Stereogenic Dialkylphosphinamides

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(9), P. 7213 - 7219

Published: April 24, 2024

Transition-metal-catalyzed enantioselective C–H functionalization has emerged as a promising method for the synthesis of P-stereogenic phosphorus compounds. However, previous reports are limited to C(sp2)–H bonds aryl phosphine derivatives. Herein, Pd(II)-catalyzed arylation more challenging C(sp3)–H toward dialkylphosphinamides is achieved through desymmetrization gem-diethyl groups. Various obtained with high enantioselectivities using 3,3′-CN2-H8-BINOL chiral ligand. The synthetic potential this methodology highlighted by gram-scale preparation and further derivatizations.

Language: Английский

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Cobalt-Catalyzed Domino Transformations via Enantioselective C–H Activation/Nucleophilic [3 + 2] Annulation toward Chiral Bridged Bicycles

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(22), P. 15576 - 15586

Published: May 16, 2024

Selective synthesis of chiral bridged (hetero)bicyclic scaffolds via asymmetric C–H activation constitutes substantial challenges due to the multiple reactivities strained bicyclic structures. Herein, we develop domino transformations through an unprecedented cobalt-catalyzed enantioselective activation/nucleophilic [3 + 2] annulation with symmetrical alkenes. The methods offer straightforward access a wide range molecules bearing [2.2.1]-bridged cores four and five consecutive stereocenters in single step. Two elaborate salicyloxazoline (Salox) ligands were synthesized based on rational design mechanistic understanding. well-defined pockets generated from coordination around trivalent cobalt catalyst direct orientation alkenes, leading excellent enantioselectivity.

Language: Английский

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Enantioselective Synthesis of 1,2‐Benzothiazine 1‐Imines via Ru^II/Chiral Carboxylic Acid‐Catalyzed C−H Alkylation/Cyclization

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(29)

Published: May 17, 2023

Sulfondiimines are diaza-analogues of sulfones with a chiral sulfur center. Compared to and sulfoximines, their synthesis transformations have so far been studied lesser extent. Here, we report the enantioselective 1,2-benzothiazine 1-imines, i.e., cyclic sulfondiimine derivatives from sulfondiimines sulfoxonium ylides via C-H alkylation/cyclization reactions. The combination [Ru(p-cymene)Cl2 ]2 newly developed spiro carboxylic acid is key achieving high enantioselectivity.

Language: Английский

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Cobalt-Catalyzed Enantioselective C–H Annulation of Benzylamines with Alkynes: Application to the Modular and Asymmetric Syntheses of Bioactive Molecules

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: unknown

Published: Nov. 2, 2023

The transition metal-catalyzed enantioselective C-H functionalization strategy has revolutionized the logic of natural product synthesis. However, previous applications have heavily relied on use noble metal catalysts such as rhodium and palladium. Herein, we report efficient synthesis C1-chiral 1,2-dihydroisoquinolines (DHIQs) via C-H/N-H annulation picolinamides with alkynes catalyzed by a more sustainable cheaper 3d catalyst, cobalt(II) acetate tetrahydrate. A wide range enantiomerically enriched DHIQs were obtained in good yields excellent enantioselectivities (up to 98% yield >99% ee). robustness synthetic potential this method demonstrated modular asymmetric syntheses several tetrahydroisoquinoline alkaloids, including (S)-norlaudanosine, (S)-laudanosine, (S)-xylopinine, (S)-sebiferine, (S)-cryptostyline II, key intermediates (+)-solifenacin, FR115427, (+)-NPS R-568.

Language: Английский

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Asymmetric Dearomatization of Indoles through Cobalt‐Catalyzed Enantioselective C−H Functionalization Enabled by Photocatalysis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: June 20, 2024

Photocatalysis holds a pivotal position in modern organic synthesis, capable of inducing novel reactivities under mild and environmentally friendly reaction conditions. However, the merger photocatalysis transition-metal-catalyzed asymmetric C-H activation as an efficient sustainable method for construction chiral molecules remains elusive challenging. Herein, we develop cobalt-catalyzed enantioselective enabled by visible-light photoredox catalysis, providing synergistic catalytic strategy dearomatization indoles with high levels enantioselectivity (96 % to >99 ee). Mechanistic studies indicate that excited photocatalyst was quenched divalent cobalt species presence Salox ligand, leading formation catalytically active Co(III) complex. Moreover, stoichiometric reactions cobaltacycle intermediate indole suggest irradiation visible light also play critical role step.

Language: Английский

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