Cobaltaelectro‐Catalyzed C–H Activation for Central and Axial Double Enantio‐Induction DOI Creative Commons
Tristan von Münchow, Yi‐Ru Liu, Rahul Parmar

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(31)

Published: May 17, 2024

Abstract In den letzten Jahren hat sich die enantioselektive Elektrokatalyse zunehmend als eine effektive Methode für nachhaltige molekulare Synthese herausgestellt. Trotz unbestreitbarer Fortschritte bleiben Strategien zur Kontrolle über zwei unterschiedliche stereogene Elemente mit hoher Selektivität schwer fassbar. Im Gegensatz dazu beschreiben wir hier elektrochemische Cobalt‐katalysierte C−H‐Aktivierungen, welche Installation chiraler stereogener Zentren zusammen einer chiralen Achse Enantio‐ und Diastereoselektivität ermöglichen. Die entwickelte elektrokatalytische Strategie erlaubte C−H/N−H‐Aktivierungen/Anellierungen cyclischen acyclischen Alkenen gewährte einen direkten Zugang zu vielseitigen sowohl zentralen auch atropo‐chiralen Dihydroisochinolinonen gepaart der wertvollen Wasserstoffbildungsreaktion. Studien Atropo‐Stabilität erhaltenen Verbindungen demonstrierten, dass äußerst milden Bedingungen, gewährleistet durch elektrokatalytischen Prozess, entscheidend hohen erzielten Stereoselektivitäten waren.

Atroposelective catalysis DOI

Tanno A. Schmidt,

Valeriia Hutskalova,

Christof Sparr

et al.

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: 8(7), P. 497 - 517

Published: June 18, 2024

Language: Английский

Citations

16
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

2
Cobaltaelectro‐Catalyzed C–H Activation for Central and Axial Double Enantio‐Induction DOI Creative Commons
Tristan von Münchow, Yi‐Ru Liu, Rahul Parmar

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(31)

Published: May 17, 2024

In recent years, enantioselective electrocatalysis has surfaced as an increasingly-effective platform for sustainable molecular synthesis. Despite indisputable progress, strategies that allow the control of two distinct stereogenic elements with high selectivity remain elusive. contrast, we, herein, describe electrochemical cobalt-catalyzed C-H activations enable installation chiral centers along a axis levels enantio- and diastereoselectivities. The developed strategy allowed C-H/N-H activations/annulations cyclic non-cyclic alkenes providing expedient access to various central well atropo-chiral dihydroisoquinolinones paired valuable hydrogen evolution reaction. Studies on atropo-stability obtained compounds demonstrated exceedingly mild conditions ensured by electrocatalytic process were key achieved stereoselectivities.

Language: Английский

Citations

11
Electrochemical enabled cobalt catalyzed enantioselective C-H acyloxylation of aryl phosphamide with carboxylic acid DOI

Xuying Xia,

Changdi Zheng,

Yunfei Hang

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(14), P. 8323 - 8329

Published: Jan. 1, 2024

We described here the first example of cobalt-electro-catalyzed enantioselective C–H acyloxylation arylphosphinamides with carboxylic acids to generate P-stereogenic scaffolds.

Language: Английский

Citations

9
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
Atroposelective Synthesis of Pyridoindolones Bearing Two Remote Distinct C–N Axes through Cobalt-Catalyzed Enantioselective C–H Activation DOI
Pu‐Fan Qian, Yanxuan Wu,

Jia-Heng Hu

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 13, 2025

C–N axially chiral compounds represent an important class of atropisomers that are prevalent in bioactive and material molecules. Despite recent advances synthetic methodologies, the asymmetric construction featuring multiple axes has been rarely explored, significantly limiting their further applications. Herein, we report a novel atroposelective synthesis diaxially pyridoindolones both six–five six–six through cobalt-catalyzed C–H annulation. This approach demonstrates exceptional efficiency, yielding diverse array with excellent yields atroposelectivities (60 examples, up to >99% yield, ee, >20:1 dr). Mechanistic studies revealed stereochemistry were generated fixed simultaneously during cyclometalation step, along unexpected amplification effect. The practicality this protocol is underscored by successful gram-scale syntheses various transformations, including formation phosphine ligand. Notably, photoluminescence quantum (ΦF 0.99) positive solvatochromism observed, coupled significant chiroptical properties, underscoring potential applications these organic fluorescent materials.

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
Simultaneous construction of inherent and axial chirality by cobalt-catalyzed enantioselective C-H activation of calix[4]arenes DOI Creative Commons
Tong Li, Yanbo Zhang, Cong Du

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Sept. 3, 2024

Language: Английский

Citations

6
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
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