RhI, IrIII ,and CoIII Complexes with Atropchiral Biaryl Cyclopentadienyl Ligands: Syntheses, Structures, and Catalytic Activities DOI
Coralie Duchemin, Gints Šmits, Nicolai Cramer

et al.

Organometallics, Journal Year: 2019, Volume and Issue: 38(20), P. 3939 - 3947

Published: July 16, 2019

Chiral cyclopentadienyl (Cpx) group 9 metal complexes have become versatile catalysts for a variety of efficient enantioselective C–H functionalizations. Atropchiral binaphthyl-derived Cpx ligands having tuning options at the 3,3′-positions present robust choice catalyst, giving high enantioselectivities and good reactivities. Herein, we report streamlined syntheses binaphthyl backbone that feature new substituents 3,3′-positions: namely, trimethylsilyl, I, Br. We introduce as well with atropchiral MeO-biphenyl backbone. All are smoothly complexed rhodium(I) salts. The CpxRhI obtained were systematically mapped by X-ray crystal analysis in order to collect steric parameters might guide rational selection chiral ligand reactions. catalytic performances evaluated two RhIII-catalyzed functionalizations benchmark transformations. In both cases, simpler access provided superior reactivity enantioselectivity. Additionally, related CpxCoIII CpxIrIII equipped developed prepared characterized.

Language: Английский

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

248
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
Chiral Cyclopentadienyl Cobalt(III) Complexes Enable Highly Enantioselective 3d-Metal-Catalyzed C–H Functionalizations DOI

Kristers Ozols,

Yun‐Suk Jang,

Nicolai Cramer

et al.

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(14), P. 5675 - 5680

Published: March 22, 2019

The synthesis of a set cobalt(III)-complexes equipped with trisubstituted chiral cyclopentadienyl ligands is reported, and their steric electronic parameters are mapped. application potential these complexes for asymmetric C-H functionalizations 3d-metals shown by the dihydroisoquinolones from N-chlorobenzamides broad range alkenes. transformation proceeds excellent enantioselectivities up to 99.5:0.5 er high regioselectivities. observed values outperform best rhodium(III)-based methods this reaction type. Moreover, challenging substrates such as alkyl alkenes also react regio- enantioselectivities.

Language: Английский

Citations

193
Iron- and cobalt-catalyzed C(sp3)–H bond functionalization reactions and their application in organic synthesis DOI
Yungen Liu,

Tingjie You,

Hai‐Xu Wang

et al.

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(15), P. 5310 - 5358

Published: Jan. 1, 2020

This review highlights the developments in iron and cobalt catalyzed C(sp3)–H bond functionalization reactions with emphasis on their applications organic synthesis, i.e. natural products pharmaceuticals synthesis and/or modification.

Language: Английский

Citations

164
Cobalt‐Catalyzed Annulation Reactions via C−H Bond Activation DOI Open Access
Sekar Prakash, Ramajayam Kuppusamy, Chien‐Hong Cheng

et al.

ChemCatChem, Journal Year: 2017, Volume and Issue: 10(4), P. 683 - 705

Published: Nov. 1, 2017

Abstract Considerable research attention has been directed towards the use of first‐row transition metals in organic synthesis. The more abundant, and less expensive cobalt is considered to be an effective alternative for second third‐row noble metals, especially C−H bond functionalization reactions. In this Minireview, we will summarize features, recent achievements Co‐catalyzed directing group assisted activation/cyclization reactions their mechanistic insights.

Language: Английский

Citations

151
Thioamide‐Directed Cobalt(III)‐Catalyzed Selective Amidation of C(sp3)−H Bonds DOI

Peng Wen Tan,

Adrian M. Mak, Michael B. Sullivan

et al.

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 56(52), P. 16550 - 16554

Published: Oct. 28, 2017

A mild, oxidant-free, and selective Cp*CoIII -catalyzed amidation of thioamides with robust dioxazolone amidating agents via C(sp3 )-H bond activation to generate the desired amidated products is reported. The method efficient allows for C-H a wide range functionalized aryl-, heteroaryl-, alkyl-substituted dioxazolones under conditions. observed regioselectivity towards primary supported by computational studies cyclometalation proposed proceed means an external carboxylate-assisted concerted metalation/deprotonation mechanism. reported rare example use directing group other than commonly used pyridine quinolone classes functionalization first exploit thioamides.

Language: Английский

Citations

145
Recent advances in cobalt-catalysed C–H functionalizations DOI

Alessio Baccalini,

Stefania Vergura,

Pravas Dolui

et al.

Organic & Biomolecular Chemistry, Journal Year: 2019, Volume and Issue: 17(48), P. 10119 - 10141

Published: Jan. 1, 2019

Ready availability, low cost and toxicity of cobalt salts have redirected the attention researchers away from noble metals, such as Pd, Rh, Ir, towards Co in field C-H functionalization. In this context, examples Co-catalysed functionalization exponentially grown over last few decades. This present review focuses on most recent developments C(sp2)-H C(sp3)-H functionalizations. Included is also a comprehensive overview enantioselective transformations.

Language: Английский

Citations

123
Chiral 2-Aryl Ferrocene Carboxylic Acids for the Catalytic Asymmetric C(sp3)–H Activation of Thioamides DOI

Daichi Sekine,

Kazuki Ikeda,

Seiya Fukagawa

et al.

Organometallics, Journal Year: 2019, Volume and Issue: 38(20), P. 3921 - 3926

Published: July 29, 2019

Enantioselective C–H functionalization reactions using trivalent group 9 metals (Co, Rh, Ir) have been investigated mainly on the basis of development well-designed chiral cyclopentadienyl (Cp) ligands. Although it has recently demonstrated that carboxylic acids combined with achiral Cp-type ligands can enable highly enantioselective reactions, structural diversity applied remains limited. Here, we report 2-aryl ferrocene acids, which are easily obtained from diastereoselective ortho lithiation and Suzuki–Miyaura coupling, serve as external sources for Cp*CoIII-catalyzed C(sp3)–H amidation α-aryl thioamides dioxazolones.

Language: Английский

Citations

103
Recent Advances in [Cp*MIII] (M = Co, Rh, Ir)‐Catalyzed Intramolecular Annulation Through C–H Activation DOI
Augustin Péneau, Catherine Guillou, Laurent Chabaud

et al.

European Journal of Organic Chemistry, Journal Year: 2018, Volume and Issue: 2018(42), P. 5777 - 5794

Published: March 15, 2018

This review aims to summarize the recent advances in field of Cp*M III (Co, Rh, Ir)‐catalyzed C–H activation followed by subsequent intramolecular reaction. approach has allowed synthesis valuable heterocycles with high structural diversity and complexity, including polycyclic macrocyclic compounds. In this review, a particular attention been made nature coupling partner (alkene, alkyne, etc) its connection either aryl (or vinyl) group or directing group. Hence, different types transformation can occur, involving one two cyclizations depending on Finally, we discuss some mechanistical aspects (role external internal oxidation, account for formation cyclic structures.

Language: Английский

Citations

98
Cp*Co(III)-Catalyzed C–H Acylmethylation of Arenes by Employing Sulfoxonium Ylides as Carbene Precursors DOI

Shuying Ji,

Kelu Yan, Bin Li

et al.

Organic Letters, Journal Year: 2018, Volume and Issue: 20(18), P. 5981 - 5984

Published: Sept. 12, 2018

A Cp*Co(III)-catalyzed C-H bond functionalization of a range arenes by employing sulfoxonium ylides as carbene precursors instead diazo compounds and other has been established. This reaction is highly efficient without any additive, possesses high step atom economies, tolerates functional groups.

Language: Английский

Citations

94