Synthesis of P- and S-Stereogenic Compounds via Enantioselective C–H Functionalization DOI
Pu‐Fan Qian, Jun-Yi Li, Tao Zhou

et al.

Synthesis, Journal Year: 2022, Volume and Issue: 54(21), P. 4784 - 4794

Published: March 18, 2022

Abstract Transition metal-catalyzed enantioselective C–H functionalization has emerged as an efficient and powerful strategy to access various chiral molecules. Recently, this also provided a complementary pathway the construction of P- S-stereogenic compounds. In short review, we summarize development applications catalytic systems: Pd(II)/mono-N-protected amino acids (MPAA), Pd(0)/trivalent phosphorus ligands, cyclopentadienyl-ligated metal catalysts [CpxM(III)] (M = Rh, Ir), half-sandwich d6 Ir(III) Ru(II) with carboxylic acid (CCA) ligand, Ir(I)/chiral bidentate boryl cation, for accessing these compounds via functionalization. 1 Introduction 2 Pd(II)/Mono-N-protected Amino Acids 3 Pd(0)/Trivalent Phosphorus Chiral Ligands 4 Cyclopentadienyl-Ligated Metal Catalysts Ir) 5 Half-sandwich Carboxylic Acid Ligand 6 Ir(I)/Chiral Bidentate Boryl 7 Cation 8 Conclusion Outlook

Language: Английский

Chiral Carboxylic Acid Assisted Enantioselective C–H Activation with Achiral CpxMIII (M = Co, Rh, Ir) Catalysts DOI
Tatsuhiko Yoshino, Shigeki Matsunaga

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(11), P. 6455 - 6466

Published: May 17, 2021

Enantioselective C–H functionalization is a powerful tool for synthesizing chiral molecules. In the past few years, combination of high-valent group 9 metals with achiral Cpx ligands and carboxylic acids (CCA) has emerged as promising catalytic system to enable selective cleavage enantiotopic bonds. This Perspective summarizes background, catalyst design, applied reactions in detail, followed by discussion future directions.

Language: Английский

Citations

120
Oxygen‐Linked Cyclopentadienyl Rhodium(III) Complexes‐Catalyzed Asymmetric C−H Arylation of Benzo[h]quinolines with 1‐Diazonaphthoquinones DOI
Chongqing Pan,

Si‐Yong Yin,

Shao‐Bo Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(28), P. 15510 - 15516

Published: April 16, 2021

Abstract Chiral cyclopentadienyl rhodium (CpRh) complex‐catalyzed asymmetric C−H functionalization reactions have witnessed a significant progress in organic synthesis. In sharp contrast, the reported chiral Cp ligands are limited to C‐linked and often synthetically challenging. To address these issues, we developed novel class of tunable bearing oxygen linkers, which were efficient catalysts for arylation benzo[ h ]quinolines with 1‐diazonaphthoquinones, affording axially heterobiaryls excellent yields enantioselectivity (up 99 % yield, 98.5:1.5 er). Mechanistic studies suggest that reaction is likely proceed by electrophilic activation, followed coupling cyclometalated rhodium(III) complex 1‐diazonaphthoquinones.

Language: Английский

Citations

104
Cobalt(III)/Chiral Carboxylic Acid‐Catalyzed Enantioselective Synthesis of Benzothiadiazine‐1‐oxides via C−H Activation DOI
Yuuki Hirata,

Daichi Sekine,

Yoshimi Kato

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(28)

Published: May 2, 2022

Abstract Among sulfoximine derivatives containing a chiral sulfur center, benzothiadiazine‐1‐oxides are important for applications in medicinal chemistry. Here, we report that the combination of an achiral cobalt(III) catalyst and pseudo‐ C 2 ‐symmetric H 8 ‐binaphthyl carboxylic acid enables asymmetric synthesis from sulfoximines dioxazolones via enantioselective C−H bond cleavage. With optimized protocol, with several functional groups can be accessed high enantioselectivity.

Language: Английский

Citations

73
Designing, characterization, biological, DFT, and molecular docking analysis for new FeAZD, NiAZD, and CuAZD complexes incorporating 1-(2-hydroxyphenylazo)− 2-naphthol (H2AZD) DOI
Hany M. Abd El‐Lateef, Mai M. Khalaf, Mahmoud Kandeel

et al.

Computational Biology and Chemistry, Journal Year: 2023, Volume and Issue: 105, P. 107908 - 107908

Published: June 21, 2023

Language: Английский

Citations

45
Transition-metal-catalyzed atroposelective synthesis of axially chiral styrenes DOI
Pu‐Fan Qian, Tao Zhou, Bing‐Feng Shi

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(85), P. 12669 - 12684

Published: Jan. 1, 2023

Recent advances in the asymmetric synthesis of axially chiral styrenes catalyzed by transition metals were summarized.

Language: Английский

Citations

42
Enantioselective Synthesis of Five-Membered-Ring Atropisomers with a Chiral Rh(III) Complex DOI Creative Commons
Saad Shaaban, Houhua Li, Felix Otte

et al.

Organic Letters, Journal Year: 2020, Volume and Issue: 22(23), P. 9199 - 9202

Published: Nov. 13, 2020

Axially chiral atropisomeric compounds are widely applied in asymmetric catalysis and medicinal chemistry, efficient methods for their synthesis high demand. This applies particular to atropisomers derived from five-membered aromatic rings because lower barrier rotation among the biaryl axis limits synthesis. We report here an enantioselective C–H functionalization method using our RhJasCp complex of atropisomer types that can be accessed three different five-membered-ring heterocycles.

Language: Английский

Citations

79
Enantioselective and Diastereoselective C–H Alkylation of Benzamides: Synergized Axial and Central Chirality via a Single Stereodetermining Step DOI
Jinlei Wang, Haohua Chen,

Lingheng Kong

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(15), P. 9151 - 9158

Published: July 9, 2021

In this report, distally disposed axial and central chirality has been installed in a synergistic fashion via rhodium-catalyzed C–H alkylation of benzamides using N-arylmaleimide as the alkylating reagent, which enantio- diastereo-determining steps are merged into single one. The coupling system features mild reaction conditions, broad substrate scope, excellent diastereoselectivity. chiral induction enabled by judicious choice rhodium cyclopentadienyl catalyst that serves to control both orientation olefin unit prochiral C–N bond.

Language: Английский

Citations

65
Development of Pseudo-C2-symmetric Chiral Binaphthyl Monocarboxylic Acids for Enantioselective C(sp3)–H Functionalization Reactions under Rh(III) Catalysis DOI

Yoshimi Kato,

Luqing Lin, M. Kojima

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(7), P. 4271 - 4277

Published: March 22, 2021

Enantioselective C(sp3)–H functionalization reactions using high-valent group 9 metal catalysts with cyclopentadienyl ligands have been achieved by the introduction of appropriate chiral carboxylic acids. However, diversity acids, as well that applicable substrate structures remains limited. Herein, we report pseudo-C2-symmetric tunable acids a binaphthyl backbone and their application to enantioselective amidation 2-alkylpyridines related heteroaromatic substrates. The fixed cyclic structure pseudo-C2-symmetry developed would reduce conformational flexibility ambiguity. combination an optimal acid sterically hindered rhodium catalyst (Cp*tBuRhIII) exhibited high enantioselectivity (up 96:4 er).

Language: Английский

Citations

61
Coordination-assisted, transition-metal-catalyzed enantioselective desymmetric C–H functionalization DOI
Xin Yu, Zhuo‐Zhuo Zhang, Jun‐Long Niu

et al.

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(5), P. 1458 - 1484

Published: Jan. 1, 2022

Recent advances in transition-metal-catalyzed enantioselective desymmetric C–H functionalization are summarized.

Language: Английский

Citations

46
Ir(III)-Catalyzed Asymmetric C–H Activation/Annulation of Sulfoximines Assisted by the Hydrogen-Bonding Interaction DOI
Jun-Yi Li, Pei‐Pei Xie, Tao Zhou

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(15), P. 9083 - 9091

Published: July 14, 2022

Transition-metal-catalyzed asymmetric C–H activation reactions generally rely on the design of ligands with sterically bulky groups to create a chiral environment for enantioinduction through steric repulsion. Here we describe an Ir(III)-catalyzed enabled by noncovalent interactions. A broad range sulfur-stereogenic sulfoximines was prepared in high yields excellent enantioselectivities via activation/annulation diazo compounds. Desymmetrization, kinetic resolution, and parallel resolution are compatible this protocol. Detailed DFT calculations suggested that N–H···O hydrogen bonding interaction between sulfoximine carboxylic acid ligand crucial enantiocontrol. Moreover, iridacycle intermediates were isolated, characterized, subjected stoichiometric reactions. Computational experimental studies cleavage step rate- enantio-determining step.

Language: Английский

Citations

42