Asymmetric Counteranion‐Directed Electrocatalysis for Enantioselective Control of Radical Cation DOI Open Access

Zhenhui Xu,

Changdi Zheng,

Jie Lin

et al.

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

Published: Aug. 30, 2024

Abstract The control of enantioselectivity in radical cation reactions presents long‐standing challenges, despite a few successful examples. We introduce novel strategy asymmetric counteranion‐directed electrocatalysis to address chemistry. This concept has been successfully demonstrated two reactions: an dehydrogenative indole‐phenol [3+2] coupling and atroposelective C−H/N−H coupling. These have enabled the synthesis benzofuroindolines C−N axially chiral indoles with high yields excellent enantiomeric excesses. Detailed mechanistic studies confirmed radical‐radical mechanism. Moreover, density functional theory (DFT) calculations supported indole as pivotal intermediate, rather than neutral indolyl radical, shedding new light on underlying processes driving these reactions.

Language: Английский

Cobalt(III)-Catalyzed Enantioselective C–H Functionalization: Ligand Innovation and Reaction Development DOI
Qi‐Jun Yao, Bing‐Feng Shi

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 26, 2025

ConspectusIn contrast to precious transition metals, such as palladium and rhodium, the development of novel chiral ligands for enantioselective C-H functionalizations catalyzed by earth-abundant, cost-effective, environmentally friendly 3d metals poses substantial challenges, primarily due variable oxidation states, intricate coordination patterns, limited mechanistic insights. In this Account, we summarize our research endeavors in three types Co(III) catalysis: pseudotetrahedral achiral Cp*Co(III)/chiral carbonyl acid (CCA) catalysis, situ-generated octahedral cobalt(III) via cobalt/salicyloxazoline (Salox) Co(II)/chiral phosphoric (CPA) cooperative achieved through strategic ligand design. Our initial objective was achieve functionalization Cp*Co(III) catalysts with external ligands, aiming circumvent laborious preparation CpxCo(III) complexes. To end, developed several CCA incorporating non-covalent interactions (NCIs) a crucial design element. Next, address limitations associated lengthy synthesis Cp-ligated complexes difficulties modification, explored concept situ generation catalysis using commercially available cobalt(II) salts tailor-made ligands. This exploration led two innovative catalytic systems, namely, Co(II)/Salox Co(II)/CCA sequential catalysis. The emerged versatile strategy, demonstrating excellent enantioselectivities across range asymmetric reactions construct various molecules central, axial, planar, inherent chirality. facile single step, along ease further enhances versatility applicability approach. Moreover, successfully applied cobalt/Salox electro- photochemical-catalyzed functionalization, electrons or oxygen traceless oxidant, thereby eliminating need stoichiometric chemical oxidants. Through studies reaction developments, elucidated detailed structure-enantioselectivity relationships which are expected inform future endeavors. Finally, Co(II)/CPA enabled spiro-γ-lactams olefination/asymmetric [4 + 1] spirocyclization. Mechanistically, establishment stereochemistry occurs during cyclization where CPA serves both neutral Brønsted acid, stereoinduction independent cleavage step. We anticipate that insights advancements Account will inspire innovations drive progress metal-catalyzed reactions.

Language: Английский

Citations

3
Parametrization of κ2-N,O-Oxazoline Preligands for Enantioselective Cobaltaelectro-Catalyzed C–H Activations DOI Creative Commons
Suman Dana, Neeraj Kumar Pandit, Philipp Boos

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4450 - 4459

Published: Feb. 28, 2025

Enantioselective electrocatalyzed C–H activations have emerged as a transformative platform for the assembly of value-added chiral organic molecules. Despite recent progress, construction multiple C(sp3)-stereogenic centers via C(sp3)–C(sp3) bond formation has thus far proven to be elusive. In contrast, we herein report an annulative activation strategy, generating Fsp3-rich molecules with high levels diastereo- and enantioselectivity. κ2-N,O-oxazoline preligands were effectively employed in enantioselective cobalt(III)-catalyzed reactions. Using DFT-derived descriptors regression statistical modeling, performed parametrization study on modularity preligands. The resulted model describing ligands' selectivity characterized by key steric, electronic, interaction behaviors.

Language: Английский

Citations

1
Electrocatalytic Enantioselective Tandem C–H Indolization toward Biindolyl Atropisomers: Reaction Development and Mechanistic Insight DOI

Zhi‐Huan Peng,

Ping Huang, Ao-Long Li

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1422 - 1430

Published: Jan. 9, 2025

The electrochemical methods for asymmetric indolization are still elusive and pose a significant challenge. Taking advantage of 2-alkynylanilines as electrochemically compatible indolyl equivalents, we herein represent mild highly enantioselective electrocatalytic process tandem C–H to form 2,3′-biindolyl atropisomers along with hydrogen evolution reaction. Integrated experimental computational mechanistic studies revealed that sequential metalation/nucleophilic cyclization/reductive elimination/anodic oxidation sequence involving RhIII–RhI–RhIII catalytic cycle accounts the established transformation.

Language: Английский

Citations

0
Catalytic construction of P-stereogenic center via phosphorus-centered nucleophilic substitution DOI
Bingbing Dong, Junmin Zhang, Xiang-Yu Ye

et al.

Chinese Chemical Letters, Journal Year: 2025, Volume and Issue: unknown, P. 111052 - 111052

Published: March 1, 2025

Language: Английский

Citations

0
N–N Atropisomer Synthesis via Electrolyte- and Base-Free Electrochemical Cobalt-Catalysed C–H Annulation DOI

Jiating Cai,

Linzai Li,

Chuitian Wang

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(23), P. 11524 - 11530

Published: Jan. 1, 2024

An exogenous electrolyte- and base-free electrochemical cobalt-catalysed atroposelective C–H annulation has been established to construct N–N axially chiral isoquinolinones in excellent enantioselectivities good yields.

Language: Английский

Citations

3
Asymmetric Counteranion‐Directed Electrocatalysis for Enantioselective Control of Radical Cation DOI Open Access

Zhenhui Xu,

Changdi Zheng,

Jie Lin

et al.

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

Published: Aug. 30, 2024

The control of enantioselectivity in radical cation reactions presents long-standing challenges, despite a few successful examples. We introduce novel strategy asymmetric counteranion-directed electrocatalysis to address chemistry. This concept has been successfully demonstrated two reactions: an dehydrogenative indole-phenol [3+2] coupling and atroposelective C-H/N-H coupling. These have enabled the synthesis benzofuroindolines C-N axially chiral indoles with high yields excellent enantiomeric excesses. Detailed mechanistic studies confirmed radical-radical mechanism. Moreover, density functional theory (DFT) calculations supported indole as pivotal intermediate, rather than neutral indolyl radical, shedding new light on underlying processes driving these reactions.

Language: Английский

Citations

2
Recent Advances in the Synthesis of P-Stereogenic Compounds via Desymmetrization Strategy DOI

Guotao Lin,

Jian Xu, Qiuling Song

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(12), P. 3621 - 3621

Published: Jan. 1, 2024

Language: Английский

Citations

1
Paired Electrocatalysis-Enabled Cross Coupling of Sulfinamides with Olefins toward the Synthesis of Vinyl Sulfoximines DOI
Tao Liu,

Yan Tang,

Jiyuan Guo

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(40), P. 8463 - 8467

Published: Oct. 2, 2024

We present here a novel paired electrocatalysis-enabled convenient synthesis of the (

Language: Английский

Citations

0
Asymmetric Counteranion‐Directed Electrocatalysis for Enantioselective Control of Radical Cation DOI Open Access

Zhenhui Xu,

Changdi Zheng,

Jie Lin

et al.

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

Published: Aug. 30, 2024

Abstract The control of enantioselectivity in radical cation reactions presents long‐standing challenges, despite a few successful examples. We introduce novel strategy asymmetric counteranion‐directed electrocatalysis to address chemistry. This concept has been successfully demonstrated two reactions: an dehydrogenative indole‐phenol [3+2] coupling and atroposelective C−H/N−H coupling. These have enabled the synthesis benzofuroindolines C−N axially chiral indoles with high yields excellent enantiomeric excesses. Detailed mechanistic studies confirmed radical‐radical mechanism. Moreover, density functional theory (DFT) calculations supported indole as pivotal intermediate, rather than neutral indolyl radical, shedding new light on underlying processes driving these reactions.

Language: Английский

Citations

0