Applications of Chiral Cyclopentadienyl (Cpx) Metal Complexes in Asymmetric Catalysis DOI Creative Commons
Saad Shaaban, Caitlin Davies, Herbert Waldmann

et al.

European Journal of Organic Chemistry, Journal Year: 2020, Volume and Issue: 2020(42), P. 6512 - 6524

Published: July 21, 2020

Metal complexes containing cyclopentadienyl (Cp) ligands are versatile and robust catalysts widely applied in organic synthesis. During the last two decades chiral Cp x have been a variety of enantioselective transformations. Often associated with Group 9 metals (Co, Rh, Ir), also used combination early transition‐metals rare‐earth elements. In this minireview asymmetric reactions that successfully steered ligand metal discussed according to coordinated. Several designs diverse array reactions, particular C–H functionalisation, binaphthyl‐derived leading field. Challenges these derive from need for their multi‐step synthesis, recently new were designed, which can be accessed shorter sequences readily available starting materials.

Language: Английский

Rh(III)-Catalyzed Asymmetric Synthesis of Axially Chiral Biindolyls by Merging C–H Activation and Nucleophilic Cyclization DOI
Miaomiao Tian, Dachang Bai, Guangfan Zheng

et al.

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(24), P. 9527 - 9532

Published: June 4, 2019

Enantiomeric access to pentatomic biaryls is challenging due their relatively low rotational barrier. Reported herein the mild and highly enantioselective synthesis of 2,3′-biindolyls via underexplored integration C–H activation alkyne cyclization using a unified chiral Rh(III) catalyst. The reaction proceeded initial followed by cyclization. A rhodacyclic intermediate has been isolated from stoichiometric activation, which offers direct mechanistic insight.

Language: Английский

Citations

258
Enantioselective C(sp3)–H Amidation of Thioamides Catalyzed by a CobaltIII/Chiral Carboxylic Acid Hybrid System DOI

Seiya Fukagawa,

Yoshimi Kato,

Ryō Tanaka

et al.

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 58(4), P. 1153 - 1157

Published: Nov. 27, 2018

Abstract Recent advances in Cp x M III catalysis (M=Co, Rh, Ir) have enabled a variety of enantioselective C(sp 2 )−H functionalization reactions, but 3 is still largely unexplored. We describe an asymmetric amidation thioamides using achiral Co /chiral carboxylic acid hybrid catalytic system, which provides easy and straightforward access to chiral β‐amino thiocarbonyl carbonyl building blocks with quaternary carbon stereocenter.

Language: Английский

Citations

246
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

229
Transition Metal Catalyzed Enantioselective C(sp2)–H Bond Functionalization DOI
Tapas Kumar Achar,

Sudip Maiti,

Sadhan Jana

et al.

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(23), P. 13748 - 13793

Published: Nov. 12, 2020

Direct catalytic transformation of C–H bonds to new functionalities has provided a powerful strategy synthesize complex molecular scaffolds in straightforward way. Unstinting efforts the synthetic community have helped overcome long-standing major challenge regioselectivity by introducing directing group concept. However, full potential cannot be realized unless activated are stereochemically controlled. The enantioselective bond functionalization could provide an imperative tool for sustainable way synthesizing chiral scaffolds. Despite intrinsic challenges achieving stereocontrol, developed different tools order achieve stereoselective functionalization. In this review, we discuss remarkable recent advances emerging area C(sp2)–H highlight and opportunities, emphasizing techniques so far.

Language: Английский

Citations

220
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

212
Cooperative Effects between Chiral Cpx–Iridium(III) Catalysts and Chiral Carboxylic Acids in Enantioselective C−H Amidations of Phosphine Oxides DOI

Yun‐Suk Jang,

Michael Dieckmann,

Nicolai Cramer

et al.

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 56(47), P. 15088 - 15092

Published: Sept. 22, 2017

Abstract An enantioselective C−H amidation of phosphine oxides by using an iridium(III) catalyst bearing atropchiral cyclopentadienyl (Cp x ) ligand is reported. A very strong cooperative effect between the chiral Cp and a phthaloyl tert‐leucine enabled transformation. Matched–mismatched cases different acid enantiomers are shown. The amidated P‐chiral arylphosphine formed in yields up to 95 % with excellent enantioselectivities 99:1 er. Enantiospecific reduction provides access valuable phosphorus(III) compounds.

Language: Английский

Citations

175
Cp*Co(III)/MPAA-Catalyzed Enantioselective Amidation of Ferrocenes Directed by Thioamides under Mild Conditions DOI
Yanhua Liu, Pengxiang Li, Qi‐Jun Yao

et al.

Organic Letters, Journal Year: 2019, Volume and Issue: 21(6), P. 1895 - 1899

Published: March 6, 2019

Cp*Cobalt(III)-catalyzed enantioselective C-H amidation of ferrocenes using monoprotected amino acids (MPAAs) as chiral ligands was developed. The reaction performed under mild conditions in high yields (up to 97%) with moderate enantioselectivity 77.5:22.5 er), providing a promising strategy create planar chirality via base-metal-catalyzed activation.

Language: Английский

Citations

169
Rhodium-Catalyzed Asymmetric C–H Functionalization Reactions DOI
Chen‐Xu Liu,

Si‐Yong Yin,

Fangnuo Zhao

et al.

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

Citations

120
Electrooxidative palladium- and enantioselective rhodium-catalyzed [3 + 2] spiroannulations DOI Creative Commons
Wen Wei, Alexej Scheremetjew, Lutz Ackermann

et al.

Chemical Science, Journal Year: 2022, Volume and Issue: 13(9), P. 2783 - 2788

Published: Jan. 1, 2022

Despite indisputable progress in the development of electrochemical transformations, electrocatalytic annulations for synthesis biologically relevant three-dimensional spirocyclic compounds has as yet not been accomplished. In sharp contrast, herein, we describe palladaelectro-catalyzed C-H activation/[3 + 2] spiroannulation alkynes by 1-aryl-2-naphthols. Likewise, a cationic rhodium(iii) catalyst was shown to enable electrooxidative [3 spiroannulations via formal C(sp3)-H activations. The versatile featured broad substrate scope, employing electricity green oxidant lieu stoichiometric chemical oxidants under mild conditions. An array enones and diverse spiropyrazolones, bearing all-carbon quaternary stereogenic centers were thereby accessed user-friendly undivided cell setup, with molecular hydrogen sole byproduct.

Language: Английский

Citations

72
Enantiodivergent Desymmetrization in the Rhodium(III)‐Catalyzed Annulation of Sulfoximines with Diazo Compounds DOI

Bing-Xue Shen,

Boshun Wan, Xingwei Li

et al.

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(47), P. 15534 - 15538

Published: Oct. 11, 2018

RhIII - and IrIII -catalyzed asymmetric C-H functionalization reactions of arenes have relied on the employment chiral /IrIII cyclopentadienyl catalysts, introduction carboxylic acids to achiral Cp*RhX2 integration both strategies. Despite considerable progress, each reaction only provided a specific configuration enantioenriched product when using particular catalyst. Reported in this work is enantiodivergent coupling sulfoximines with various diazo compounds by desymmetrizing annulation. The enantiodivergence was enabled judicious choice acids, enantioselectivity correlates steric bias acid sulfoximine.

Language: Английский

Citations

153