Cobalt-Catalyzed Enantioselective C–H Annulation with Alkenes DOI
Dandan Yang, Xian Zhang, Xinghua Wang

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(7), P. 4250 - 4260

Published: March 13, 2023

Herein, we disclose an efficient cobalt-catalyzed enantioselective C–H activation and annulation of benzamides with alkenes. This transformation is facilitated via the commercially available cobalt(II) catalyst in presence easily prepared chiral salicyl-oxazoline (Salox) ligand, which provides facile access to (R) or (S) enantiomers dihydroisoquinolone derivatives. It noticeable that reaction proceeded efficiently within extremely short time from 10 30 min under mild conditions. A broad range alkenes bear various functional substituents have been shown good compatibility deliver targeted products high yields enantioselectivities (51 examples, up 98% yield 99% ee). The gram scale experiment removal directing group further demonstrate practicability this protocol potential industrial applications. Density theory calculations elucidate mechanism, spin-state change olefin insertion step accelerates subsequent C–N reductive elimination, identified as stereo-determining step. AIM analysis indicates π interactions are vital for controlling switching stereoselectivity.

Language: Английский

3d Transition Metals for C–H Activation DOI
Parthasarathy Gandeepan, Thomas Müller, Daniel Zell

et al.

Chemical Reviews, Journal Year: 2018, Volume and Issue: 119(4), P. 2192 - 2452

Published: Nov. 27, 2018

C–H activation has surfaced as an increasingly powerful tool for molecular sciences, with notable applications to material crop protection, drug discovery, and pharmaceutical industries, among others. Despite major advances, the vast majority of these functionalizations required precious 4d or 5d transition metal catalysts. Given cost-effective sustainable nature earth-abundant first row metals, development less toxic, inexpensive 3d catalysts gained considerable recent momentum a significantly more environmentally-benign economically-attractive alternative. Herein, we provide comprehensive overview on until summer 2018.

Language: Английский

Citations

1966
Enantioselective C−H Activation with Earth‐Abundant 3d Transition Metals DOI
Joachim Loup, Uttam Dhawa, Fabio Pesciaioli

et al.

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(37), P. 12803 - 12818

Published: May 11, 2019

Molecular syntheses largely rely on time- and labour-intensive prefunctionalization strategies. In contrast, C-H activation represents an increasingly powerful approach that avoids lengthy of prefunctionalized substrates, with great potential for drug discovery, the pharmaceutical industry, material sciences, crop protection, among others. The enantioselective functionalization omnipresent bonds has emerged as a transformative tool step- atom-economical generation chiral molecular complexity. However, this rapidly growing research area remains dominated by noble transition metals, prominently featuring toxic palladium, iridium rhodium catalysts. Indeed, despite significant achievements, use inexpensive sustainable 3d metals in asymmetric activations is still clearly its infancy. Herein, we discuss remarkable recent progress transformations via organometallic base up to April 2019.

Language: Английский

Citations

377
Dirhodium tetracarboxylates as catalysts for selective intermolecular C–H functionalization DOI
Huw M. L. Davies, Kuangbiao Liao

Nature Reviews Chemistry, Journal Year: 2019, Volume and Issue: 3(6), P. 347 - 360

Published: May 7, 2019

Language: Английский

Citations

330
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

245
Enantioselective Pallada‐Electrocatalyzed C−H Activation by Transient Directing Groups: Expedient Access to Helicenes DOI Creative Commons
Uttam Dhawa, Cong Tian, Tomasz Wdowik

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(32), P. 13451 - 13457

Published: April 3, 2020

Abstract Asymmetric pallada‐electrocatalyzed C−H olefinations were achieved through the synergistic cooperation with transient directing groups. The electrochemical, atroposelective activations realized high position‐, diastereo‐, and enantio‐control under mild reaction conditions to obtain highly enantiomerically‐enriched biaryls fluorinated N−C axially chiral scaffolds. Our strategy provided expedient access to, among others, novel BINOLs, dicarboxylic acids helicenes of value asymmetric catalysis. Mechanistic studies by experiments computation key insights into catalyst's mode action.

Language: Английский

Citations

231
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
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
Enantioselective C H Bond Functionalizations by 3d Transition-Metal Catalysts DOI
Łukasz Woźniak, Nicolai Cramer

Trends in Chemistry, Journal Year: 2019, Volume and Issue: 1(5), P. 471 - 484

Published: April 20, 2019

Language: Английский

Citations

215
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

211
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

191