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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Cobaltaelectro-Catalyzed C–H Annulation with Allenes for Atropochiral and P-Stereogenic Compounds: Late-Stage Diversification and Continuous Flow Scale-Up

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(14), P. 9713 - 9723

Published: July 11, 2023

The 3d metallaelectro-catalyzed C-H activation has been identified as an increasingly viable strategy to access valuable organic molecules in a resource-economic fashion under exceedingly mild reaction conditions. However, the development of enantioselective is very challenging and its infancy. Here, we disclose merger cobaltaelectro-catalyzed with asymmetric catalysis for highly annulation allenes. A broad range C-N axially chiral P-stereogenic compounds were thereby obtained good yields up 98% high enantioselectivities >99% ee. practicality this approach was demonstrated by diversification complex bioactive drug well decagram scale electrocatalysis continuous flow.

Language: Английский

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Synthesis of CF₃–Isoquinolinones and Imidazole-Fused CF₃–Isoquinolinones Based on C–H Activation-Initiated Cascade Reactions of 2-Aryloxazolines

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(14), P. 10180 - 10196

Published: July 4, 2024

Presented herein are novel syntheses of CF

Language: Английский

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Recent advances in the synthesis of trifluoromethyl-containing heterocyclic compounds via trifluoromethyl building blocks

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(31), P. 6246 - 6276

Published: Jan. 1, 2024

Recent advances in the preparation of trifluoromethyl-containing heterocyclics via trifluoromethyl building block strategies over period from 2019 to present are systematically summarized and discussed.

Language: Английский

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Rhodium-catalyzed annulative approach to N–N axially chiral biarylsviaC–H activation and dynamic kinetic transformation

Chemical Science, Journal Year: 2023, Volume and Issue: 14(32), P. 8564 - 8569

Published: Jan. 1, 2023

N-N axially chiral biaryls represent a rarely explored class of atropisomeric compounds. We hereby report rhodium-catalyzed enantioselective [4 + 2] oxidative annulation internal alkynes with benzamides bearing two classes directing groups. The coupling occurs under mild conditions

Language: Английский

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C–N Axially Chiral Heterobiaryl Isoquinolinone Skeletons Construction via Cobalt-Catalyzed Atroposelective C–H Activation/Annulation

Organic Letters, Journal Year: 2023, Volume and Issue: 25(34), P. 6240 - 6245

Published: Aug. 18, 2023

Herein, the atroposelective construction of isoquinolinones bearing a C-N chiral axis has been successfully developed via Co-catalyzed C-H bond activation and annulation process. This conversion can be effectively carried out in an environmentally friendly oxygen atmosphere to generate target axially frameworks with excellent reactivities enantioselectivities (up >99% ee) absence any additives. Additionally, current protocol proved alternative approach for axial architectures fabrication under electrochemical conditions cobalt/Salox catalysis, this strategy allowed efficient atom-economical synthesis various mild reaction conditions.

Language: Английский

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Electrochemical Enantioselective C–H Annulation by Achiral Rhodium(III)/Chiral Brønsted Base Domino Catalysis

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8160 - 8167

Published: May 10, 2024

Rhodium(III)-catalyzed enantioselective C–H activation has emerged as a powerful tool for assembling enabling chiral molecules. However, this approach is significantly hampered by the cumbersome synthetic routes preparing rhodium catalysts. In sharp contrast, we herein report on an electrochemical domino catalysis system that exploits achiral Cp*-rhodium catalyst along with easily accessible Brønsted base activation/annulation reaction of alkenes benzoic acids. Our strategy offers environmentally benign and most user-friendly synthetically useful phthalides in good enantioselectivity, employing electricity sustainable oxidant.

Language: Английский

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Rhodium(III)-Catalyzed Coupling of Quinolin-8-carboxaldehydes with CF₃–Imidoyl Sulfoxonium Ylides by Chelation-Assisted C(sp²)-H Bond Activation for the Synthesis of Trifluoromethyl-Substituted Enaminones

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(15), P. 10736 - 10747

Published: July 18, 2024

A rhodium(III)-catalyzed aldehydic C(sp

Language: Английский

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Palladium‐Catalyzed Atroposelective Kinetic C−H Olefination and Allylation for the Synthesis of C−B Axial Chirality

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(47)

Published: Oct. 16, 2023

Abstract The direct C−H functionalization of 1,2‐benzazaborines, especially asymmetric version, remains a great challenge. Here we report palladium‐catalyzed enantioselective olefination and allylation reactions 1,2‐benzazaborines. This approach is kinetic resolution (KR), providing various C−B axially chiral 2‐aryl‐1,2‐benzazaborines 3‐substituted in generally high yields with excellent enantioselectivities (selectivity (S) factor up to 354). synthetic potential this reaction showcased by late‐stage modification complex molecules, scale‐up reaction, applications.

Language: Английский

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Rh(III)‐Catalyzed Cascade Cyclization of 2‐Aryl‐3H‐indoles and CF₃‐Imidoyl Sulfoxonium Ylides Toward Trifluoroacetimidoyl‐Substituted 11H‐Isoindolo[2,1‐a]indoles

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(22), P. 3855 - 3860

Published: Oct. 18, 2023

Abstract A rhodium(III)‐catalyzed C−H activation/[4+1] annulation of 2‐aryl‐3 H ‐indoles and CF 3 ‐substituted imidoyl sulfoxonium ylides (TFISYs) has been achieved, producing a wide variety trifluoroacetimidoyl‐substituted 11 ‐isoindolo[2,1‐a]indoles in 51–86% yields. The cascade reaction involves imidoylmethylation, tautomerization AgOAc‐mediated C−N bond formation sequence. could be scaled up to 2 mmol scale.

Language: Английский

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