Cp*Co(III)-Catalyzed Synthesis of Isoquinolones via Controlled Annulation of Primary Arylamides with Internal Alkynes DOI
Saksham Mishra,

Akanksha Singh Baghel,

Amit Kumar

и другие.

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 13, 2024

In this study, we present the first cobalt(III)-catalyzed direct synthesis of isoquinolones from readily available primary arylamides and internal alkynes through a controlled oxidative C-H/N-H annulation reaction. This innovative protocol eliminates need for expensive transition metal salts external auxiliaries, producing desired mono-annulated product exclusively while accommodating wide range substrates. Preliminary mechanistic studies highlight critical role copper oxide in facilitating transformation. Additionally, peripheral modifications core isoquinolone rings have been performed to synthesize complex heterocyclic systems.

Язык: Английский

Unleashing the potentiality of metals: synergistic catalysis with light and electricity DOI
Zhengjia Shen, Jia‐Lin Tu, Binbin Huang

и другие.

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(14), С. 4024 - 4040

Опубликована: Янв. 1, 2024

This review provides a comprehensive overview of metal catalysis in photo-electrochemical systems, discussing reaction mechanisms and offering prospects for this triadic catalytic mode.

Язык: Английский

Процитировано

13
Parametrization of κ2-N,O-Oxazoline Preligands for Enantioselective Cobaltaelectro-Catalyzed C–H Activations DOI Creative Commons
Suman Dana, Neeraj Kumar Pandit, Philipp Boos

и другие.

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4450 - 4459

Опубликована: Фев. 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.

Язык: Английский

Процитировано

1
Enantioselective Cobaltaphotoredox-Catalyzed C–H Activation DOI Creative Commons
Yang Xu, Lin Ye, Simon L. Homölle

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(34), С. 24105 - 24113

Опубликована: Авг. 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-

Язык: Английский

Процитировано

8
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

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Июнь 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.

Язык: Английский

Процитировано

4
Nickel(II)/Salox-Catalyzed Enantioselective C–H Functionalization DOI Creative Commons
Jiahao Chen, Qi‐Jun Yao,

Ming-Yu Zhong

и другие.

ACS Central Science, Год журнала: 2025, Номер 11(1), С. 127 - 135

Опубликована: Янв. 2, 2025

Recently, nickel catalysts have garnered considerable attention for their efficacy and versatility in asymmetric catalysis, attributed to distinctive properties. However, the use of cost-effective sustainable divalent C–H activation/asymmetric alkene insertion poses significant challenges due intricate control stereochemistry transformation tetracoordinate C–Ni(II) intermediate. Herein, we report a Ni(II)-catalyzed enantioselective C–H/N–H annulation with oxabicyclic alkenes. This protocol offers straightforward access chiral [2,2,1]-bridged bicyclic compounds bearing four consecutive stereocenters high enantioselectivity (up 96% ee). The development sterically hindered salicyloxazoline (Salox) ligand, TMS-Salox, is key success this protocol. Mechanistic investigations unveiled that Ni(III)-metalacyclic intermediate was formed through situ oxidation achiral organometallic Ni(II) species coordination Salox ligand. process led creation tailored pocket guides approach alkenes, thereby influencing determining stereochemistry.

Язык: Английский

Процитировано

0
Mechanistic Investigations of Cobalt-Catalyzed, Aminoquinoline-Directed C(sp2)–H Bond Functionalization DOI
Lukass Lukasevics,

George N. Oh,

Xiqu Wang

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 10, 2025

Monoanionic, bidentate-auxiliary-directed, cobalt-catalyzed C–H bond functionalization has become a very useful tool in organic synthesis. A comprehensive investigation into isolated organometallic intermediates and their reactivity within the catalytic cycle is lacking. We report here mechanistic studies of cobalt-catalyzed, aminoquinoline-directed C(sp2)–H functionalization. number Co(III) have been structurally characterized, including, for first time aminoquinoline system, complexes arising from migratory insertion cobalt–carbon bonds. The stoichiometric reactions cobalt(III) aryls with alkenes, alkynes, carbon monoxide, cyclic secondary amines, benzamides explored. oxidation state cobalt product-forming step depends on nature coupling component. Specifically, annulation alkynes carbonylation CO likely proceed via Co(I)/Co(III) cycle. Carbon–hydrogen alkenes as well benzamide homocoupling, (formally) Co(IV) species involve oxidatively induced reductive elimination.

Язык: Английский

Процитировано

0
Cp*Co(III)-catalyzed ortho-alkylation/alkenylation of anilides DOI
Yongqi Yu, Jiajia Yu, Ying Li

и другие.

Organic & Biomolecular Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

A highly practical and efficient Cp*Co( iii )-catalyzed regioselective C–H alkylation/alkenylation of anilides with maleimides acrylates was developed, during which a weakly coordinating amide group functioned as the directing group.

Язык: Английский

Процитировано

0
Catalytic Enantioselective [4+1]-Annulation of Carboxylic Acids with Cyclopropenes DOI

Marimuthu Bakkiyaraj,

Pazhamalai Anbarasan

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 12, 2025

An efficient asymmetric synthesis of 3-vinylphthalides has been accomplished through rhodium-catalyzed [4+1]-annulation arylcarboxylic acids with cyclopropenes involving C–H bond functionalization. The method exhibited excellent compatibility for various functional groups and offered diverse substituted in yield enantioselectivity. Synthetic application control experiments were also performed to demonstrate the utility understand reaction pathway.

Язык: Английский

Процитировано

0
Progress on Cobalt-Catalyzed C(sp2)—H Activation for the Construction of Nitrogen-Containing Benzo Heterocycles DOI
Xun Tian, Guogang Deng, Xiaodong Yang

и другие.

Chinese Journal of Organic Chemistry, Год журнала: 2025, Номер 45(2), С. 655 - 655

Опубликована: Янв. 1, 2025

Язык: Английский

Процитировано

0
Enantioselective Cobalt(III)-Catalyzed [4 + 1] Annulation of Benzamides: Cyclopropenes as One-Carbon Synthons DOI Creative Commons
Lenin Kumar Verdhi, Matthew D. Wodrich, Nicolai Cramer

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 28, 2025

A chiral cyclopentadienyl cobalt(III)-catalyzed enantioselective [4 + 1] annulation of N-chlorobenzamides with cyclopropenes is reported. The cobalt catalyst engages in the C-H activation as well promotes C-C bond cleavage cyclopropene, rendering it a one-carbon unit for annulation. reaction efficiently constructs biologically relevant isoindolinones selectivities up to 99:1 er and >20:1 E/Z ratios. cobalt(III) displays unique orthogonal reactivity profile delivering products, whereas its rhodium(III) homologue more classical 2] pattern. Computational studies reveal origin these divergences.

Язык: Английский

Процитировано

0