Lewis Acid Catalyzed Three‐Component Carbofunctionalization of Styrenes with Diacyl Peroxides and Nucleophiles DOI Open Access

Shuang–Long Li,

Ren Wang, Jiajie Chen

et al.

Advanced Synthesis & Catalysis, Journal Year: 2022, Volume and Issue: 365(1), P. 17 - 22

Published: Dec. 13, 2022

Abstract A Lewis acid catalyzed carbofunctionalization of styrenes with diacyl peroxides and nucleophiles, including amines, indoles, trimethoxybenzenes, carboxylic acid, has been accomplished. wide range primary, secondary, tertiary alkyl generated from inexpensive aliphatic acids serve as both simple alkylating reagents internal oxidants for the synthesis value‐added 1,1‐diarylalkanes, esters in moderate to good yields. This protocol features site selectivity, broad substrate scope, mild reaction conditions. magnified image

Language: Английский

Enantioselective Radical Reactions Using Chiral Catalysts DOI
Shovan Mondal, Frédéric Dumur, Didier Gigmès

et al.

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(6), P. 5842 - 5976

Published: Jan. 24, 2022

Benefiting from the impressive increase in fundamental knowledge, last 20 years have shown a continuous burst of new ideas and consequently plethora catalytic methods for enantioselective radical reactions. This review aims to provide complete survey progress achieved over this latter period. The first part focuses on use chiral organocatalysts, these include catalysts covalently linked substrate those that interact with by weaker interactions like hydrogen bonds. second is devoted transition-metal redox catalysis which organized according increasing atomic number first-row transition metals (Ti, Cr, Fe, Mn, Co, Ni, Cu). Bioinspired manganese- iron-mediated hydroxylations oxidations are also discussed. A specific section dedicated reactivity Ru, Rh, Ir complexes as Lewis acids special focus at metal. Absorption photons result different events such energy transfer, single-electron hydrogen-atom transfer facilitating formation radicals. Organocatalysis has been successfully combined photocatalysts, opened pathways enlarging precursors available. merger photocatalysis organo- or metalla-photocatalysis brought novelty allowed discovery large original transformations. enzyme-catalyzed reactions involving intermediates largely benefit visible-light irradiation included review. provides comprehensive inventory goal detailing reaction mechanisms involved transformations any nonspecialist could find their own creativity invent yet unknown applications.

Language: Английский

Citations

265
Asymmetric three-component olefin dicarbofunctionalization enabled by photoredox and copper dual catalysis DOI Creative Commons

Peng‐Zi Wang,

Yuan Gao, Jun Chen

et al.

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: March 22, 2021

Abstract The intermolecular three-component alkene vicinal dicarbofunctionalization (DCF) reaction allows installation of two different carbon fragments. Despite extensive investigation into its ionic chemistry, the enantioseletive radical-mediated versions DCF reactions remain largely unexplored. Herein, we report an intermolecular, enantioselective radical olefins enabled by merger addition and cross-coupling using photoredox copper dual catalysis. Key to success this protocol relies on chemoselective acyl cyanoalkyl radicals, generated in situ from redox-active oxime esters a photocatalytic N-centered iminyl radical-triggered C-C bond cleavage event, onto alkenes form new radicals. Single electron metalation such newly formed radicals TMSCN-derived L1 Cu(II)(CN) 2 complex leads asymmetric cross-coupling. This process proceeds under mild conditions, tolerates diverse range functionalities synthetic handles, leading valuable optically active β –cyano ketones alkyldinitriles, respectively, highly manner (>60 examples, up 97% ee).

Language: Английский

Citations

112
Photoelectrochemical Asymmetric Catalysis Enables Enantioselective Heteroarylcyanation of Alkenes via C–H Functionalization DOI
Xiao‐Li Lai, Hai‐Chao Xu

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(34), P. 18753 - 18759

Published: Aug. 15, 2023

The asymmetric difunctionalization of alkenes, a method transforming readily accessible alkenes into enantioenriched chiral structures high value, has long been focal point organic synthesis. Despite tremendous efforts in this domain, it remains considerable challenge to devise enantioselective oxidative dicarbofunctionalization even though these transformations can utilize stable and unfunctionalized functional group donors. In context, we report herein photoelectrocatalytic for the heteroarylcyanation aryl which employs heteroarenes through C-H functionalization. photoelectrochemical catalysis (PEAC) combines photoredox electrocatalysis facilitate formation two C-C bonds operating via hydrogen (H2) evolution obviating need external chemical oxidants.

Language: Английский

Citations

63
Copper-catalysed asymmetric radical cyanation DOI
Fei Wang, Pinhong Chen, Guosheng Liu

et al.

Nature Synthesis, Journal Year: 2022, Volume and Issue: 1(2), P. 107 - 116

Published: Jan. 31, 2022

Language: Английский

Citations

69
Copper-Catalyzed Asymmetric Functionalization of Vinyl Radicals for the Access to Vinylarene Atropisomers DOI
Liang Fu, Xin Chen, Wenzheng Fan

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(24), P. 13476 - 13483

Published: June 10, 2023

A novel asymmetric radical strategy for the straightforward synthesis of atropisomerically chiral vinyl arenes has been established herein, proceeding through copper-catalyzed atroposelective cyanation/azidation aryl-substituted radicals. Critical to success relay process is capture highly reactive radicals with L*Cu(II) cyanide or azide species. Moreover, these axially vinylarene products can be easily transformed into enriched amides and amines, enantiomerically benzyl nitriles via an axis-to-center chirality transfer process, pure organocatalyst chemo-, diastereo-, enantioselective (4 + 2) cyclization reaction.

Language: Английский

Citations

35
Enantioselective Four-Component Arylsulfonylcyanation of Vinylarenes via the Insertion of SO2 Enabled by SOgen as SO2 Surrogate DOI
Lei Chen, Xuemei Zhang, Mi Zhou

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(17), P. 10764 - 10770

Published: Aug. 18, 2022

A copper-catalyzed four-component enantioselective arylsulfonylcyanation of vinylarenes has been developed that enables easy access to a variety chiral β-sulfonyl nitriles with up 95% yield and 96% ee. The reaction utilizes bench-stable SO2 surrogate (SOgen), takes place under mild conditions, exhibits good substrate scope functional group compatibility. Control experiments show the use SOgen as is key achieving excellent reactivities enantioselectivities. Preliminary mechanistic data indicates this vinylarene 1,2-difunctionalization likely proceeds by radical pathway. exemplifies rare case catalysis involving gaseous SO2.

Language: Английский

Citations

34
Enantioselective cyanation of propargylic C–H bonds via cooperative photoredox and copper catalysis DOI Creative Commons

Yunshun Deng,

Ronghua Lu,

Pinhong Chen

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(31), P. 4656 - 4659

Published: Jan. 1, 2023

Herein, we report an enantioselective cyanation of propargylic C-H bonds by combining photoredox catalysis with a copper-catalyzed radical relay in which the was generated intramolecular 1,5-HAT process. This reaction provides easy access to optically pure propargyl nitrile compounds under mild conditions.

Language: Английский

Citations

18
Recent Advances in Theoretical Studies on Cu-Mediated Bond Formation Mechanisms Involving Radicals DOI
Ji‐Ren Liu,

Guo-Xiong Xu,

Li‐Gao Liu

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(4), P. 2429 - 2454

Published: Feb. 1, 2024

Copper-catalyzed radical transformations establish a powerful toolkit to construct versatile complex organic compounds. The copper-mediated bond formation step of radicals plays critical role in controlling chemo- and stereoselectivity copper-catalyzed transformation reactions. This involves three possible pathways: ion-type formation, substitution, reductive elimination. review highlights the recent advances theoretical studies on mechanisms models selectivity Cu-mediated radical-involved providing general mechanistic comprehension this key elementary copper catalysis.

Language: Английский

Citations

7
Arylcyanation of Styrenes by Photoactive Electron Donor–Acceptor Complexes/Copper Catalysis DOI
Qilong Wu, Xufeng Li, Jie Ma

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(37), P. 7949 - 7955

Published: Sept. 11, 2024

A novel electron donor-acceptor (EDA) complex/copper catalysis model has been proposed for the construction of 2,3-diarylpropionitriles under visible light conditions. The developed protocol proceeds via intermolecular charge transfer between photoactive EDA complex dibutamine (DBA), aryl thianthrenium salts, and trimethylsilyl cyanide (TMSCN), followed by a copper catalytic cycle. UV-vis absorption measurements confirm participation complexes as reactive intermediates. This three-component process smoothly in presence pharmaceutically relevant core structures sensitive functional groups, which offers possibility precise editing drug molecules with important scaffolds.

Language: Английский

Citations

7
Recent Developments in Copper(I)‐Catalyzed Enantioselective Alkynylation Reactions via a Radical Process DOI

Xueling Mo,

R.T. Guo, Guozhu Zhang

et al.

Chinese Journal of Chemistry, Journal Year: 2022, Volume and Issue: 41(4), P. 481 - 489

Published: Oct. 7, 2022

Comprehensive Summary Alkynes are one of the most significant functional groups in organic chemistry and great efforts have been made to explore efficient approach for construction chiral alkynes. The asymmetric C(sp 3 )–C(sp) cross‐coupling provides a complementary strategy through radical‐initiated process. However, stereocontrol highly reactive unstable radical intermediate has challenge decades. To address this problem, variety ligands developed initiating reaction achieving enantiocontrol alkyl radicals. This review summarizes recent developments copper‐catalyzed enantioselective alkynylation prochiral radicals their brief mechanistic studies.

Language: Английский

Citations

22