Stereocontrolled Synthesis of Chiral Helicene‐Indenido ansa‐ and Half‐Sandwich Metal Complexes and Their Use in Catalysis DOI Creative Commons
Ivo Starý, Tereza Edlová, Jiří Rybáček

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 64(1)

Published: Sept. 26, 2024

Abstract Despite recent tremendous progress in the synthesis of nonplanar chiral aromatics, and helicenes particular, their conversion to half‐sandwich or sandwich transition metal complexes still lags behind, although they represent an attractive family modular underexplored architectures with a potential catalytic use. In this work, starting from various helicene‐indene proligands, we prepared enantio‐ diastereopure oxa[6]‐ oxa[7]helicene‐indenido Rh I III oxa[7]helicene‐bisindenido ansa ‐metallocene Fe II complex. To document use, oxahelicene‐indenido were employed as catalysts enantioselective C−H arylation benzo[ h ]quinolines 1‐diazonaphthoquinones afford series axially biaryls mostly good high yields up 96 : 4 er . Thus, developed stereocontrolled helicene‐indenido ‐ complexes, successfully demonstrated first use such helicene Cp‐related catalysis, described unusual sequence efficient central‐to‐helical‐to‐planar‐to‐axial chirality transfer.

Language: Английский

Enantioselective Synthesis of Indole-Fused Polycycles Bearing Four Consecutive Stereocenters via Rhodium Catalysis DOI
Ting Yu, Weiqi Liu, Beijing Chen

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 3, 2025

Indole-fused polycycles are common in natural products and bioactive molecules, yet their concise efficient synthesis remains challenging, especially for compounds with multiple stereocenters. Herein, we report the application of a chiral CpxRhIII catalyst enantioselective C–H activation/[4+2] annulation indoles bicyclic alkenes. This catalytic system exhibits high enantioselectivity broad functional group tolerance operates under benign conditions. The scope this methodology encompasses variety substrates, delivering novel polycyclic four consecutive stereocenters bridged ring good to excellent yields remarkable enantioselectivities (≤1:99 er). approach facilitates structurally diverse molecules that retain integrity while introducing chirality. More importantly, 3ab significantly inhibited proliferation CESS Kasumin-1 cells IC50 values 0.76 0.28 μM, respectively. In addition, has been demonstrated as an effective agent promoting apoptosis cells.

Language: Английский

Citations

1
Electrochemical Enantioselective C–H Annulation by Achiral Rhodium(III)/Chiral Brønsted Base Domino Catalysis DOI Creative Commons
Yanjun Li, Jiawei Xu, João C. A. Oliveira

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8160 - 8167

Published: May 10, 2024

Rhodium(III)-catalyzed enantioselective C–H activation has emerged as a powerful tool for assembling enabling chiral molecules. However, this approach is significantly hampered by the cumbersome synthetic routes preparing rhodium catalysts. In sharp contrast, we herein report on an electrochemical domino catalysis system that exploits achiral Cp*-rhodium catalyst along with easily accessible Brønsted base activation/annulation reaction of alkenes benzoic acids. Our strategy offers environmentally benign and most user-friendly synthetically useful phthalides in good enantioselectivity, employing electricity sustainable oxidant.

Language: Английский

Citations

7
Application of Planar Chiral Cyclopentadienyl Rhodium Catalysts without Chiral Substituents in Asymmetric C—H Activation DOI
Yu Zou,

Weicong Guo,

Jun Wang

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 45(2), P. 466 - 466

Published: Jan. 1, 2025

Language: Английский

Citations

0
[2.2]Benzoindenophane‐Based Chiral Indenyl Ligands: Design, Synthesis, and Applications in Asymmetric C−H Activation DOI

Weicong Guo,

Ji‐Jun Jiang, Jun Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(32)

Published: May 23, 2024

Abstract Development of chiral indenyl ligands for asymmetric C−H activation is a longstanding challenge, and extremely few successes have been achieved. In this paper, we describe class readily accessible, facilely tunable user‐friendly featuring [2.2]benzoindenophane skeleton via divergent synthesis strategy. The corresponding rhodium catalysts were successfully applied in the reaction O‐Boc hydroxybenzamide with alkenes to give various dihydroisoquinolone products (up 97 % yield, up 98 ee). Moreover, carboxylic acids alkynes was also accomplished, providing range axially isocoumarins 99 94 Notably, represents first example enantioselective transition metal catalyzed C(sp 2 )−H activation/oxidative coupling benzoic internal construct isocoumarins. Given many attractive features ligands, such as convenient synthesis, high tunability exclusive face‐selectivity coordination, its applications more catalytic other catalysis are foreseen.

Language: Английский

Citations

3
Chiral Bis(binaphthyl) Cyclopentadienyl Ligands for Rhodium-Catalyzed Desymmetrization of Diarylmethanes via Selective Arene Coordination DOI

Wen‐Qiang Wu,

Pei‐Pei Xie, Leyao Wang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 18, 2024

Owing to substantial advances in the past several decades, transition-metal-catalyzed asymmetric reactions have garnered considerable attention as pivotal methods for constructing chiral molecules from abundant, readily available achiral counterparts. These are largely attributed development of ligands that control stereochemistry through steric repulsion and other noncovalent interactions between functional groups or prochiral centers on substrates. However, stereocontrol weakens dramatically with increasing distance reaction site group center. Herein, we report a symphonic strategy remote Rh(III)-catalyzed benzylic C-H bond addition diarylmethanes which two aryl motifs differ at

Language: Английский

Citations

1
Enantiospecific Synthesis of Planar Chiral Rhodium and Iridium Cyclopentadienyl Complexes: Enabling Streamlined and Computer-Guided Access to Highly Selective Catalysts for Asymmetric C–H Functionalizations DOI Creative Commons
Sebastian Young Ye, Aragorn Laverny, Matthew D. Wodrich

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 6, 2024

Chiral cyclopentadienyl (Cp

Language: Английский

Citations

1
Available strategies for the synthesis of indenes for metal complex catalysis DOI
Vladimir B. Kharitonov, Dmitry A. Loginov

Russian Chemical Bulletin, Journal Year: 2024, Volume and Issue: 73(10), P. 2787 - 2800

Published: Oct. 1, 2024

Language: Английский

Citations

0
[2.2]Benzoindenophane‐Based Chiral Indenyl Ligands: Design, Synthesis, and Applications in Asymmetric C−H Activation DOI

Weicong Guo,

Ji‐Jun Jiang, Jun Wang

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(32)

Published: May 23, 2024

Abstract Development of chiral indenyl ligands for asymmetric C−H activation is a longstanding challenge, and extremely few successes have been achieved. In this paper, we describe class readily accessible, facilely tunable user‐friendly featuring [2.2]benzoindenophane skeleton via divergent synthesis strategy. The corresponding rhodium catalysts were successfully applied in the reaction O‐Boc hydroxybenzamide with alkenes to give various dihydroisoquinolone products (up 97 % yield, up 98 ee). Moreover, carboxylic acids alkynes was also accomplished, providing range axially isocoumarins 99 94 Notably, represents first example enantioselective transition metal catalyzed C(sp 2 )−H activation/oxidative coupling benzoic internal construct isocoumarins. Given many attractive features ligands, such as convenient synthesis, high tunability exclusive face‐selectivity coordination, its applications more catalytic other catalysis are foreseen.

Language: Английский

Citations

0
Stereocontrolled Synthesis of Chiral Helicene‐Indenido ansa‐ and Half‐Sandwich Metal Complexes and Their Use in Catalysis DOI Creative Commons
Ivo Starý, Tereza Edlová, Jiří Rybáček

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 137(1)

Published: Sept. 26, 2024

Abstract Despite recent tremendous progress in the synthesis of nonplanar chiral aromatics, and helicenes particular, their conversion to half‐sandwich or sandwich transition metal complexes still lags behind, although they represent an attractive family modular underexplored architectures with a potential catalytic use. In this work, starting from various helicene‐indene proligands, we prepared enantio‐ diastereopure oxa[6]‐ oxa[7]helicene‐indenido Rh I III oxa[7]helicene‐bisindenido ansa ‐metallocene Fe II complex. To document use, oxahelicene‐indenido were employed as catalysts enantioselective C−H arylation benzo[ h ]quinolines 1‐diazonaphthoquinones afford series axially biaryls mostly good high yields up 96 : 4 er . Thus, developed stereocontrolled helicene‐indenido ‐ complexes, successfully demonstrated first use such helicene Cp‐related catalysis, described unusual sequence efficient central‐to‐helical‐to‐planar‐to‐axial chirality transfer.

Language: Английский

Citations

0
Stereocontrolled Synthesis of Chiral Helicene‐Indenido ansa‐ and Half‐Sandwich Metal Complexes and Their Use in Catalysis DOI Creative Commons
Ivo Starý, Tereza Edlová, Jiří Rybáček

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 64(1)

Published: Sept. 26, 2024

Abstract Despite recent tremendous progress in the synthesis of nonplanar chiral aromatics, and helicenes particular, their conversion to half‐sandwich or sandwich transition metal complexes still lags behind, although they represent an attractive family modular underexplored architectures with a potential catalytic use. In this work, starting from various helicene‐indene proligands, we prepared enantio‐ diastereopure oxa[6]‐ oxa[7]helicene‐indenido Rh I III oxa[7]helicene‐bisindenido ansa ‐metallocene Fe II complex. To document use, oxahelicene‐indenido were employed as catalysts enantioselective C−H arylation benzo[ h ]quinolines 1‐diazonaphthoquinones afford series axially biaryls mostly good high yields up 96 : 4 er . Thus, developed stereocontrolled helicene‐indenido ‐ complexes, successfully demonstrated first use such helicene Cp‐related catalysis, described unusual sequence efficient central‐to‐helical‐to‐planar‐to‐axial chirality transfer.

Language: Английский

Citations

0