Rhodium‐Catalyzed Enantioselective Oxidative [3+2] Annulation of Arenes and Azabicyclic Olefins through Twofold C−H Activation DOI

Ruijie Mi,

Guangfan Zheng, Zisong Qi

et al.

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(49), P. 17666 - 17670

Published: Sept. 24, 2019

Abstract C−H bond activation is mostly limited to ortho selectivity. Activation of both and meta bonds constitutes a particularly important strategy for annulation, but has rarely been studied in enantioselective systems. Reported herein rhodium(III)‐catalyzed asymmetric [3+2] transannulation arenes with 7‐azabenzonorbornadienes. Two distinct classes have identified as substrates, the coupling proceeded high enantioselectivity excellent diastereoselectivity through sequential bonds.

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

245
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

211
Modern Stereoselective Synthesis of Chiral Sulfinyl Compounds DOI Creative Commons
Elżbieta Wojaczyńska, Jacek Wojaczyński

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(10), P. 4578 - 4611

Published: April 29, 2020

Chiral sulfinyl compounds, sulfoxides, sulfoximines, sulfinamides, and other derivatives, play an important role in asymmetric synthesis as versatile auxiliaries, ligands, catalysts. They are also recognized pharmacophores found already marketed well-sold drugs (e.g., esomeprazole) used drug design. This review is devoted to the modern methods of preparation derivatives enantiopure or enantiomerically enriched form. Selected new approaches leading racemic products for which variant can be developed future mentioned well.

Language: Английский

Citations

194
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
Efficient Synthesis of Sulfur-Stereogenic Sulfoximines via Ru(II)-Catalyzed Enantioselective C–H Functionalization Enabled by Chiral Carboxylic Acid DOI
Tao Zhou, Pu‐Fan Qian, Jun-Yi Li

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(18), P. 6810 - 6816

Published: April 28, 2021

Ru(II)-catalyzed enantioselective C-H functionalization involving an enantiodetermining cleavage step remains undeveloped. Here we describe a activation/annulation of sulfoximines with α-carbonyl sulfoxonium ylides using novel class chiral binaphthyl monocarboxylic acids as ligands, which can be easily and modularly prepared from 1,1'-binaphthyl-2,2'-dicarboxylic acid. A broad range sulfur-stereogenic were in high yields excellent enantioselectivities (up to 99% yield ee) via desymmetrization, kinetic resolution, parallel resolution. Furthermore, the resolution products transformed sulfoxides key intermediates for kinase inhibitors.

Language: Английский

Citations

164
Generation of Heteroatom Stereocenters by Enantioselective C–H Functionalization DOI

Johannes Diesel,

Nicolai Cramer

ACS Catalysis, Journal Year: 2019, Volume and Issue: 9(10), P. 9164 - 9177

Published: Aug. 30, 2019

C–H functionalization has been established as an efficient way to generate molecular complexity. The formation of stereogenic carbon atoms by asymmetric seen tremendous progress over the past decade. More recently, direct catalytic modification bonds powerfully applied noncarbon centers, which constitute a key design element biologically active molecules and chiral ligands for catalysis. This area was opened seminal report describing enantioselective silicon stereocenter. It rapidly expanded with advances in phosphorus(V) centers. Moreover, routes sulfur oxidation states IV (sulfoxides) VI (sulfoximines) have disclosed. Herein, we discuss methods using selective remote heteroatom center via inner-sphere activation mechanism.

Language: Английский

Citations

153
Divergent Synthesis of Tunable Cyclopentadienyl Ligands and Their Application in Rh-Catalyzed Enantioselective Synthesis of Isoindolinone DOI

Wenjun Cui,

Zhijie Wu, Qing Gu

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(16), P. 7379 - 7385

Published: April 7, 2020

A series of rhodium complexes bearing sterically and electronically tunable cyclopentadienyl ligands, prepared by utilizing Co2(CO)8-mediated [2+2+1] cyclization as a key step, were synthesized. In the presence 2.5 mol% CpmRh4, unprecedented enantioselective [4+1] annulation reaction benzamides alkenes was achieved with broad substrate scope under mild conditions, providing variety isoindolinones excellent regio- enantioselectivity (up to 94% yield, 97:3 er). Preliminary mechanistic studies suggest that involves an oxidative Heck intramolecular alkene hydroamination reaction.

Language: Английский

Citations

142
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

118