Enantioselective copper-catalyzed azidation/click cascade reaction for access to chiral 1,2,3-triazoles DOI Creative Commons
Lingfeng Jiang,

Shaohua Wu,

Yuxuan Jiang

и другие.

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июнь 10, 2024

Chiral 1,2,3-triazoles are highly attractive motifs in various fields. However, achieving catalytic asymmetric click reactions of azides and alkynes for chiral triazole synthesis remains a significant challenge, mainly due to the limited systems substrate scope. Herein, we report an enantioselective azidation/click cascade reaction N-propargyl-β-ketoamides with readily available potent azido transfer reagent via copper catalysis, which affords variety up 99% yield 95% ee under mild conditions. Notably, 1,5-disubstituted triazoles that have not been accessed by previous also prepared good functional group tolerance.

Язык: Английский

Copper-catalyzed radical relay in C(sp3)–H functionalization DOI
Zuxiao Zhang, Pinhong Chen, Guosheng Liu

и другие.

Chemical Society Reviews, Год журнала: 2022, Номер 51(5), С. 1640 - 1658

Опубликована: Янв. 1, 2022

Radical-involved transition metal (TM) catalysis has greatly enabled new reactivities in recent decades. Copper-catalyzed radical relay offers enormous potential C(sp3)-H functionalization which combines the unique regioselectivity of hydrogen atom transfer (HAT) and versatility copper-catalyzed cross-coupling. More importantly, significant progress been achieved asymmetric C-H through judicious ligand design. This tutorial review will highlight advances this rapidly growing area, we hope survey inspire future strategic developments for selective functionalization.

Язык: Английский

Процитировано

236
Photoinduced Copper-Catalyzed Asymmetric C–O Cross-Coupling DOI
Jun Chen, Yujie Liang,

Peng‐Zi Wang

и другие.

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(33), С. 13382 - 13392

Опубликована: Авг. 10, 2021

The construction of carbon–heteroatom bonds is one the most active areas research in organic chemistry because function molecules often derived from presence heteroatoms. Although considerable advances have recently been achieved radical-involved catalytic asymmetric C–N bond formation, there has little progress corresponding C–O bond-forming processes. Here, we describe a photoinduced copper-catalyzed cross-coupling readily available oxime esters and 1,3-dienes to generate diversely substituted allylic with high regio- enantioselectivity (>75 examples; up 95% ee). reaction proceeds at room temperature under excitation by purple light-emitting diodes (LEDs) features use single, earth-abundant copper-based chiral catalyst as both photoredox for radical generation source induction coupling. Combined experimental density functional theory (DFT) computational studies suggest formation π-allylcopper complexes redox-active bifunctional reagents through radical–polar crossover process.

Язык: Английский

Процитировано

156
Photoinduced Copper-Catalyzed Late-Stage Azidoarylation of Alkenes via Arylthianthrenium Salts DOI Creative Commons
Yuan Cai, Sagnik Chatterjee, Tobias Ritter

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(25), С. 13542 - 13548

Опубликована: Июнь 12, 2023

The arylethylamine pharmacophore is conserved across a range of biologically active natural products and pharmaceuticals, particularly in molecules that act on the central nervous system. Herein, we present photoinduced copper-catalyzed azidoarylation alkenes at late stage with arylthianthrenium salts, allowing access to highly functionalized acyclic (hetero)arylethylamine scaffolds are otherwise difficult access. A mechanistic study consistent rac-BINAP-CuI-azide (2) as photoactive catalytic species. We show utility new method by expedient synthesis racemic melphalan four steps through C-H functionalization.

Язык: Английский

Процитировано

82
A General Platform for Visible Light Sulfonylation Reactions Enabled by Catalytic Triarylamine EDA Complexes DOI
Juan D. Lasso, Durbis J. Castillo‐Pazos, Jan Michael Salgado

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(4), С. 2583 - 2592

Опубликована: Янв. 17, 2024

Catalytic electron donor–acceptor (EDA) complexes have recently emerged as a powerful and sustainable alternative to iridium- ruthenium-based photoredox synthetic methods. Yet, these remain underexplored reliant on the use of meticulously designed acceptors that require previous installation. Herein, we report novel EDA complex employing tris(4-methoxyphenyl) amine catalytic donor for sulfonylation alkenes using inexpensive readily available sulfonyl chlorides. Applying this operationally simple, visible-light-mediated general platform, both redox-neutral net-reductive functionalization more than 60 substrates, encompassing vinylic or allylic sulfonylation, hydrosulfonylation, sulfamoylation activated unactivated alkynes.

Язык: Английский

Процитировано

44
Iron-Catalyzed Enantioselective Radical Carboazidation and Diazidation of α,β-Unsaturated Carbonyl Compounds DOI
Wen Liu, Maoping Pu, Jun He

и другие.

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(30), С. 11856 - 11863

Опубликована: Июль 23, 2021

Azidation of alkenes is an efficient protocol to synthesize organic azides which are important structural motifs in synthesis. Enantioselective radical azidation, as a useful strategy install C–N3 bond, remains challenging due the inherently instability and unique structure radicals. Here, we disclose enantioselective carboazidation diazidation α,β-unsaturated ketones amides catalyzed by chiral N,N′-dioxide/Fe(OTf)2 complexes. An array substituted was transformed corresponding α-azido carbonyl derivatives good excellent enantioselectivities, benefiting preparation α-amino ketones, vicinal amino alcohols, diamines. Control experiments mechanistic studies proved pathway reaction process. The DFT calculations showed that azido transferred intermediate via intramolecular five-membered transition state with internal nitrogen Fe–N3 species.

Язык: Английский

Процитировано

77
Iron‐Catalyzed Radical Asymmetric Aminoazidation and Diazidation of Styrenes DOI
Daqi Lv,

Qiao Sun,

Huan Zhou

и другие.

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(22), С. 12455 - 12460

Опубликована: Март 22, 2021

Abstract Asymmetric aminoazidation and diazidation of alkenes are straightforward strategies to build value‐added chiral nitrogen‐containing compounds from feedstock chemicals. They provide direct access organoazides complement enantioselective diamination. Despite the advances in non‐asymmetric reactions, asymmetric or based on acyclic systems has not been previously reported. Here we describe iron‐catalyzed intermolecular styrenes. The method is practically useful requires relatively low loading catalyst ligand. With mild reaction conditions, can be completed a 20 mmol scale. Studies mechanism suggest that proceeds via radical pathway involves stereocontrol an free which probably takes place through group transfer mechanism.

Язык: Английский

Процитировано

72
Copper-catalysed asymmetric radical cyanation DOI
Fei Wang, Pinhong Chen, Guosheng Liu

и другие.

Nature Synthesis, Год журнала: 2022, Номер 1(2), С. 107 - 116

Опубликована: Янв. 31, 2022

Язык: Английский

Процитировано

69
An iron-catalyzed multicomponent reaction of cycloketone oxime esters, alkenes, DABCO·(SO2)2 and trimethylsilyl azide DOI
Jun Zhang,

Junwei Wu,

Xiaotong Chang

и другие.

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(4), С. 917 - 922

Опубликована: Янв. 1, 2022

The synthesis of β-azidosulfones starting from alkenes, cycloketone oxime esters, trimethylsilyl azide and a sulfur dioxide surrogate DABCO·(SO 2 ) under iron catalysis is developed.

Язык: Английский

Процитировано

45
Site- and Enantioselective Manganese-Catalyzed Benzylic C–H Azidation of Indolines DOI
Min Cao, Hongliang Wang,

Yingang Ma

и другие.

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(33), С. 15383 - 15390

Опубликована: Авг. 11, 2022

A manganese-catalyzed highly site- and enantioselective benzylic C–H azidation of indolines has been described. The practical method is applicable for a tertiary bond with good functional group tolerance, allowing facile access to structurally diverse azide-containing in high efficiency excellent site-, chemo-, enantioselectivity. generality the was further demonstrated by secondary range indolines. allows straightforwardly enantioselectively install variety nitrogen-based groups bioactive molecules at C3 position indoline frameworks through post-azidation manipulations. Gram-scale synthesis also demonstrated, highlighting synthetic potential method. Mechanistic studies combined experiments computations elucidated reaction mechanism origins stereoselectivity.

Язык: Английский

Процитировано

45
Copper-Catalyzed Asymmetric Functionalization of Vinyl Radicals for the Access to Vinylarene Atropisomers DOI
Liang Fu, Xin Chen, Wenzheng Fan

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(24), С. 13476 - 13483

Опубликована: Июнь 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.

Язык: Английский

Процитировано

35