Advances in Asymmetric Electrochemical Synthesis DOI

Chun Gao,

Xin Liu, Minghui Wang

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(3), P. 673 - 673

Published: Jan. 1, 2024

Language: Английский

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
Enantioselective C–H annulations enabled by either nickel- or cobalt-electrocatalysed C–H activation for catalyst-controlled chemodivergence DOI Creative Commons
Tristan von Münchow, Neeraj Kumar Pandit, Suman Dana

et al.

Nature Catalysis, Journal Year: 2025, Volume and Issue: unknown

Published: March 7, 2025

Language: Английский

Citations

1
Reversal of Regioselectivity in Asymmetric C−H Bond Annulation with Bromoalkynes under Cobalt Catalysis** DOI

Abir Das,

Rajib Mandal,

Harihara Subramanian Ravi Sankar

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(6)

Published: Dec. 14, 2023

Abstract Metal‐catalyzed asymmetric C−H bond annulation strategy offers a versatile platform, allowing the construction of complex P‐chiral molecules through atom‐ and step‐economical fashion. However, regioselective insertion π‐coupling partner between M−C with high enantio‐induction remain elusive. Using commercially available Co(II) salt chiral‐Salox ligands, we demonstrate an unusual protocol for regio‐reversal, enantioselective phosphinamide bromoalkyne desymmetrization. The reaction proceeds ligand‐assisted enantiodetermining cyclocobaltation followed by Co−C, subsequent reductive elimination, halogen exchange carboxylate resulted in P‐stereogenic compounds excellent ee (up to >99 %). isolation cobaltacycle involved catalytic cycle outcome control experiments provide support plausible mechanism.

Language: Английский

Citations

17
Enantioselective Cobaltaphotoredox-Catalyzed C–H Activation DOI Creative Commons
Yang Xu, Lin Ye, Simon L. Homölle

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(34), P. 24105 - 24113

Published: Aug. 15, 2024

The quest for sustainable strategies in molecular synthesis has spurred the emergence of photocatalysis as a particularly powerful technique. In recent years, application this context greatly promoted development asymmetric catalysis. Despite impressive advances, enantioselective photoinduced strong arene C-H activations by cobalt catalysis remain unexplored. Herein, we report strategy that merges organic photoredox and cobalt-catalyzed activation, enabling regio- stereoselective dual functionalization indoles an fashion. Thereby, assembly various chiral indolo[2,3-

Language: Английский

Citations

8
Recent advances in synthetic organic electrochemistry using flow systems DOI Creative Commons
David Cantillo

Current Opinion in Electrochemistry, Journal Year: 2024, Volume and Issue: 44, P. 101459 - 101459

Published: Feb. 6, 2024

The recent resurgence of electrochemical methods in organic synthesis has also boosted the interest use flow electrolysis cells. Flow electrolyzers are essential tools for scale up processes due to their high electrode surface area reactor volume ratio, which only depends on interelectrode gap regardless size. Recent literature topic reveals that cell a very common tool lab provide gram amounts material, often enabling lower voltages and decrease supporting electrolyte needed reaction. Scale-up multi-100 g kilogram been demonstrated both using numbering sizing strategies.

Language: Английский

Citations

7
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
A review of recent advances in electrochemical and photoelectrochemical late-stage functionalization classified by anodic oxidation, cathodic reduction, and paired electrolysis DOI Creative Commons
Nian Li, Ruzal Sitdikov, Ajit Prabhakar Kale

et al.

Beilstein Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 20, P. 2500 - 2566

Published: Oct. 9, 2024

With the resurgence of electrosynthesis in organic chemistry, there is a significant increase number routes available for late-stage functionalization (LSF) drugs. Electrosynthetic methods, which obviate need hazardous chemical oxidants or reductants, offer unprecedented control reactions through continuous variation applied potential and possibility combination with photochemical processes. This capability substantial advantage performing electrochemical photoelectrochemical LSF. Ultimately, these protocols are poised to become vital component medicinal chemist's toolkit. In this review, we discuss that have been demonstrated be applicable LSF pharmaceutical drugs, their derivatives, natural substrates. We present analyze representative examples illustrate electrochemistry photoelectrochemistry valuable molecular scaffolds.

Language: Английский

Citations

6
A Dual Cobalt‐Photoredox Catalytic Approach for Asymmetric Dearomatization of Indoles with Aryl Amides via C−H Activation DOI

Abir Das,

Subramani Kumaran,

Harihara Subramanian Ravi Sankar

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: June 19, 2024

Abstract In this study, we unveil a novel method for the asymmetric dearomatization of indoles under cobalt/photoredox catalysis. By strategically activating C−H bonds amides and subsequent migratory insertion π‐bonds present in indole as reactive partner, achieve syn ‐selective tetrahydro‐5 H ‐indolo[2,3‐ c ]isoquinolin‐5‐one derivatives with excellent yields enantiomeric excesses up to >99 %. The developed operates without metal oxidant, relying solely on oxygen oxidant employing an organic dye photocatalyst irradiation. Control experiments stoichiometric studies elucidate reversible nature enantiodetermining activation step, albeit not being rate‐determining. This study only expands horizon cobalt‐catalyzed bond functionalization, but also showcases potential synergy between cobalt photoredox catalysis enabling synthesis complex molecules.

Language: Английский

Citations

4
Pd-catalyzed enantioselective and regioselective asymmetric hydrophosphorylation and hydrophosphinylation of enynes DOI

Yanxin Jiang,

Kwai Wun Cheng,

Zhiping Yang

et al.

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: unknown, P. 110231 - 110231

Published: July 1, 2024

Language: Английский

Citations

4
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