Dual-Ligand-Enabled Ir(III)-Catalyzed Enantioselective C–H Amidation for the Synthesis of Chiral Sulfoxides DOI
Wentan Liu, Wu Yang,

Jiefeng Zhu

et al.

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(13), P. 7207 - 7215

Published: June 15, 2020

A rational designed Ir(III)-catalyzed enantioselective C–H amidation of dibenzyl sulfoxides through desymmetrization and parallel kinetic resolution is demonstrated. An Ir(III) complex equipped with a t-butyl cyclopentadienyl ligand paired modified chiral proline enables the highly sulfoxide-steered bond activation, providing an efficient straightforward way to construct sulfur centers. wide range dioxazolones are compatible this process, giving access variety functionalized sulfoxide compounds synthetically attractive amide substitution groups in good yields enantioselectivities. Moreover, flexible derivatization amidated was elaborated, various types scaffolds that would be potentially useful asymmetric catalysis as bidentate tridentate ligands.

Language: Английский

C–H activation DOI
Torben Rogge, Nikolaos Kaplaneris, Naoto Chatani

et al.

Nature Reviews Methods Primers, Journal Year: 2021, Volume and Issue: 1(1)

Published: June 17, 2021

Language: Английский

Citations

433

Chiral Cyclopentadienyl Ligands: Design, Syntheses, and Applications in Asymmetric Catalysis DOI
Josep Mas‐Roselló, Ana G. Herraiz, B. Audic

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(24), P. 13198 - 13224

Published: July 16, 2020

The creation of new chiral ligands capable providing high stereocontrol in metal-catalyzed reactions is crucial modern organic synthesis. production bioactive molecules as single enantiomers increasingly required, and asymmetric catalysis with metal complexes constitutes one the most efficient synthetic strategies to access optically active compounds. Herein we offer a historical overview on development derivatives ubiquitous cyclopentadienyl ligand (CpX ), detail their successful application broad range transformations. Those include functionalization challenging C-H bonds beyond, giving an extensive catalogue valuable molecules. A critical comparison existing families, design, synthesis, complexation different metals also provided. In addition, future research directions are discussed further enhance performance CpX enantioselective catalysis.

Language: Английский

Citations

226

Diverse Approaches for Enantioselective C−H Functionalization Reactions Using Group 9 CpxMIII Catalysts DOI
Tatsuhiko Yoshino,

Shun Satake,

Shigeki Matsunaga

et al.

Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 26(33), P. 7346 - 7357

Published: Jan. 29, 2020

Transition-metal-catalyzed C-H functionalization reactions with Cp*MIII catalysts (M=Co, Rh, Ir) have found a wide variety of applications in organic synthesis. Albeit the intrinsic difficulties achieving catalytic stereocontrol using these due to their lack additional coordination sites for external chiral ligands and conformational flexibility Cp ligand, enantioselective Group 9 metal triad Cp-type been intensively studied since 2012. In this minireview, progress according type catalyst used are summarized discussed. The development Cpx complexes thereof, artificial metalloenzymes, carboxylate-assisted activations, alkylations assisted by carboxylic acids or sulfonates, transient directing groups

Language: Английский

Citations

210

Catalytic Enantioselective Functionalizations of C–H Bonds by Chiral Iridium Complexes DOI
Łukasz Woźniak, Jin-Fay Tan, Qui-Hien Nguyen

et al.

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(18), P. 10516 - 10543

Published: Sept. 8, 2020

The development of catalytic enantioselective transformations, enabling the construction complex molecular scaffolds from simple precursors, has been a long-standing challenge in organic synthesis. Recent achievements transition-metal catalyzed functionalizations carbon–hydrogen (C–H) bonds represent promising pathway toward this goal. Over last two decades, iridium catalysis evolved as valuable tool stereocontrolled synthesis chiral molecules via C–H activation. iridium-based systems with various ligand classes, well studies their reaction mechanisms, resulted dynamic progress area. This review aims to present comprehensive picture by complexes emphasis on mechanisms activation step.

Language: Английский

Citations

209

Recent Advances in Alkenyl sp2 C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications DOI
Mingzhu Lu, Jeffrey Goh, Manikantha Maraswami

et al.

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(24), P. 17479 - 17646

Published: Oct. 14, 2022

Alkenes and their derivatives are featured widely in a variety of natural products, pharmaceuticals, advanced materials. Significant efforts have been made toward the development new practical methods to access this important class compounds by selectively activating alkenyl C(sp2)–H bonds recent years. In comprehensive review, we describe state-of-the-art strategies for direct functionalization sp2 C–H C–F until June 2022. Moreover, metal-free, photoredox, electrochemical also covered. For clarity, review has divided into two parts; first part focuses on currently available using different alkene as starting materials, second describes bond easily accessible gem-difluoroalkenes material. This includes scope, limitations, mechanistic studies, stereoselective control (using directing groups well metal-migration strategies), applications complex molecule synthesis where appropriate. Overall, aims document considerable advancements, current status, emerging work critically summarizing contributions researchers working fascinating area is expected stimulate novel, innovative, broadly applicable functionalizations coming

Language: Английский

Citations

148

Recent advances in transition metal-catalyzed olefinic C–H functionalization DOI
Bingxian Liu, Lingyun Yang, Pengfei Li

et al.

Organic Chemistry Frontiers, Journal Year: 2020, Volume and Issue: 8(5), P. 1085 - 1101

Published: Dec. 23, 2020

Recent advances during 2015–2020 in the field of metal-catalyzed olefinic C–H functionalization are organized according to metal center catalyst, with an emphasis on similarities and differences among different catalysts.

Language: Английский

Citations

143

Ni-Catalyzed Asymmetric Hydrophosphination of Unactivated Alkynes DOI
Xu-Teng Liu,

Xue-Yu Han,

Yue Wu

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(30), P. 11309 - 11316

Published: July 20, 2021

The practical synthesis of P-stereogenic tertiary phosphines, which have wide applications in asymmetric catalysis, materials, and pharmaceutical chemistry, represents a significant challenge. A regio- enantioselective hydrophosphination using cheap ubiquitous alkynes catalyzed by nickel complex was designed, the toxic air-sensitive secondary phosphines were prepared situ from bench-stable phosphine oxides. This methodology has been demonstrated with unprecedented substrate scope functional group compatibility to afford electronically structurally diversified P(III) compounds. products could be easily converted into various precursors bidentate ligands organocatalysts, as well variety transition-metal complexes containing both P- metal-stereogenic centers.

Language: Английский

Citations

110

Cobalt/Salox‐Catalyzed Enantioselective C−H Functionalization of Arylphosphinamides DOI
Qi‐Jun Yao, Jiahao Chen, Hong Song

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(25)

Published: April 6, 2022

Previous methods on CoIII -catalyzed asymmetric C-H activation rely the use of tailor-made cyclopentadienyl-ligated complexes, which require lengthy steps for preparation. Herein, we report an unprecedented enantioselective functionalization enabled by a simple cobalt/salicyloxazoline (Salox) catalysis. The chiral Salox ligands can be easily prepared in one step from salicylonitrile and amino alcohols. A broad range P-stereogenic compounds were synthesized high yields with excellent enantioselectivities (45 examples, up to 99 % yield >99 ee). isolation characterization several intermediates provided insights into generation active catalytic cobalt species, action Salox, mode stereocontrol.

Language: Английский

Citations

95

Enantioselective C–H Functionalization toward Silicon-Stereogenic Silanes DOI
Chuan He, Wei Yuan

Synthesis, Journal Year: 2022, Volume and Issue: 54(08), P. 1939 - 1950

Published: Jan. 3, 2022

Abstract In recent years, transition-metal-catalyzed enantioselective C–H bond functionalization has emerged as a powerful and attractive synthetic approach to access silicon-stereogenic centers, which provides impetus for the innovation of chiral organosilicon chemistry. This short review summarizes advances in construction silanes via functionalization. We endeavor highlight great potential this methodology hope that will shed light on new perspectives inspire further research emerging area. 1 Introduction 2 Enantioselective Functionalization Induced by Oxidative Addition­ an Aryl-OTf Bond 3 Silacyclobutane 4 Directing-Group-Assisted 5 Dehydrogenative C–H/Si–H Coupling 5.1 C(sp2)–H Silylation 5.2 C(sp3)–H 6 Summary Outlook

Language: Английский

Citations

91

Palladium-catalyzed enantioselective C–H functionalization via C–H palladation DOI
Bei‐Bei Zhan, Liang Jin, Bing‐Feng Shi

et al.

Trends in Chemistry, Journal Year: 2022, Volume and Issue: 4(3), P. 220 - 235

Published: Jan. 20, 2022

Language: Английский

Citations

86