Insights into gold-catalyzed formation of aza-heterocycles using benzofuroxans as nitrene transfer reagents: mechanism and origins of chemoselectivity DOI Creative Commons
Weirong Wu,

Jiehui Liang,

Biaolin Jiang

et al.

RSC Advances, Journal Year: 2022, Volume and Issue: 12(42), P. 27483 - 27491

Published: Jan. 1, 2022

Density functional theory (DFT) calculations have been performed to reveal the mechanism of gold(i)-catalyzed annulation N-allylynamides and benzofuroxans as nitrene transfer reagents construct azaheterocyclic compounds. The calculated results revealed that reaction mainly undergoes eight processes. Among steps, intramolecular nucleophilic attack imino N atom on α-position activated gold keteniminium is a rate-determining process, which different from proposed previously by experiment. chemoselectivity products controlled competition between cyclopropanation α-imino carbenes phenyl ring carbenes, could be explained NPA charge. yields cyclopropanated product in solvents are dictated relative polarity leading energy barriers steps. present work expounds experimental observation at molecular level informative for exploring efficient syntheses 3-azabicyclo[3.1.0]hexanes.

Language: Английский

Isoxazoles as efficient alkyne amination reagents in divergent heterocycle synthesis DOI Creative Commons
Xiao-Kang Zhu, Zhe Meng, Bo Zhou

et al.

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review summarizes the latest trends and developments of isoxazole-enabled alkyne amination reactions their applications in divergent heterocycle synthesis.

Language: Английский

Citations

2

Advances in gold catalyzed synthesis of quinoid heteroaryls DOI Creative Commons

Adnan Majeed,

Ayesha Zafar,

Zanira Mushtaq

et al.

RSC Advances, Journal Year: 2024, Volume and Issue: 14(29), P. 21047 - 21064

Published: Jan. 1, 2024

Synthesis of quinoid heteroaryls via gold-catalyzed cascade protocols: recent advances and methodologies.

Language: Английский

Citations

8

Synthesis of Amide Enol 2-Iodobenzoates by the Regio- and Stereoselective Gold-Catalyzed Acyloxyalkynylation of Ynamides with Hypervalent Iodine Reagents DOI
Yaowen Liu, Martin C. Dietl, Chunyu Han

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(39), P. 7101 - 7106

Published: Sept. 22, 2022

Multisubstituted alkenes are accessible by a gold-catalyzed acyloxyalkynylation of ynamides with ethynylbenziodoxolones (EBXs) perfect atom-economy. The EBX reagents transfer both the carboxylate as well alkynyl entity. Overall, this cascade comprises in situ generation an gold(III) species, stereoselective C(sp)-C(sp2) bond formation, and C-O coupling at position ynamides. This reaction proceeds under mild conditions accepts wide range substrates. A number tetrasubstituted amide enol 2-iodobenzoates bearing different functional groups were obtained good to excellent yields. DFT calculations explain observed regioselectivity. synthetic potential was further demonstrated selected follow-up transformations.

Language: Английский

Citations

20

Copper-catalyzed asymmetric cascade diyne cyclization/Meinwald rearrangement DOI

Ji‐Jia Zhou,

Li‐Gao Liu, Zhentao Zhang

et al.

Chinese Chemical Letters, Journal Year: 2025, Volume and Issue: unknown, P. 110870 - 110870

Published: Jan. 1, 2025

Language: Английский

Citations

0

Gold‐Catalyzed Oxygen Transfer to Alkynylsulfones: A Diazo‐Free Route to 4‐Sulfonyl‐1,3‐Oxazoles DOI
Elena I. Chikunova, Dmitry Dar’in, Vadim Yu. Kukushkin

et al.

Advanced Synthesis & Catalysis, Journal Year: 2022, Volume and Issue: 364(21), P. 3697 - 3707

Published: Sept. 24, 2022

Abstract The gold‐catalyzed annulation of alkynylsulfones, involving pyridine N ‐oxides (as O ‐atom transfer reagents) and nitriles C=N synthons), comprises a diazo‐free route to valuable 4‐sulfonyl‐1,3‐oxazoles. This reaction operates under relatively mild conditions (IPrAuNTf 2 5 mol %, rt or 60 °C), number functionalities was compatible (35 examples; 14–95%). In most cases, the SO fragment, which is typically expulsed in previously reported Au‐catalyzed ‐transfers retains heterocyclic products. postulated mechanism suggests key role reactive gold α‐oxo carbene intermediates formed via transfer. magnified image

Language: Английский

Citations

14

Non-Friedländer Route to Diversely 3-Substituted Quinolines through Au(III)-Catalyzed Annulation Involving Electron-Deficient Alkynes DOI
Elena I. Chikunova, Vadim Yu. Kukushkin, Alexey Yu. Dubovtsev

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(48), P. 8756 - 8760

Published: Nov. 28, 2023

Gold(III)-catalyzed annulation of electron-deficient alkynes and 2-amino-arylcarbonyls provides general modular one-step access to a broad scope quinoline products. This highly selective reaction is useful alternative the classic Friedländer synthesis, which requires harsh conditions. In contrast, developed method works under relatively mild PicAuCl2-catalyzed conditions exhibits high functional group tolerance (40 examples; yields ≤96%). Another feature approach versatility toward other alkynes. Alkynylsulfones, alkynylcarbonyls, alkynylphosphonates, propiolonitriles, trifluoromethylated can be used as starting materials for preparation quinolines diversely substituted at position 3. On basis experimental data, we proposed mechanism in gold(III) functions strong electrophilic activator C≡C bond carbonyl group. The synthetic potential presented additionally illustrated by practical postmodifications obtained compounds, including two-step synthesis interpirdine, potent drug candidate.

Language: Английский

Citations

8

Gold‐Catalyzed Tandem Oxidation‐Migration of 3‐Propargyl Indoles: Synthesis of α‐Indol‐3‐yl α,β‐Unsaturated Carbonyls DOI Creative Commons
Lorena Renedo,

Estela Álvarez,

Marta Solas

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(9), P. 2079 - 2089

Published: March 2, 2024

Abstract α‐Indol‐3‐yl α,β‐unsaturated carbonyl compounds are synthesized from 3‐propargyl indoles, obtained by direct propargylation of via a gold‐catalyzed tandem oxidation‐1,2‐indole migration reaction in the presence pyridine N ‐oxides. Fine‐tuning catalyst and oxidant enables indoles bearing different substituents. The order oxidation indole is determined terminal or internal nature alkyne moiety. In addition, process can be coupled with additional reactions, allowing an increase molecular complexity design more elaborated reactions. this sense, derivatives alkenyl substituent at position evolve through migration‐Nazarov cyclization producing α‐indolyl cyclopentenones.

Language: Английский

Citations

2

Denitrative Formal [5 + 1] Cycloaddition of 1‐(2‐Nitrophenyl)‐2‐yn‐1‐ones with Thioacetamide under Transition Metal‐Free Conditions. Synthesis of Thiochromen‐4‐ones DOI

Yao Xu,

Wenjun Wang,

Hui Fan

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: May 31, 2024

Abstract A new strategy for thiochromen‐4‐one synthesis that relies on the denitrative formal [5+1] cycloaddition of 1‐(2‐nitrophenyl)‐2‐yn‐1‐ones with thioacetamide is described. Achieved under reaction conditions did not require transition metal catalysis, nor exclusion air or moisture, suggested to involve exploiting propensity undergo hydrolysis basic conditions. This follows by addition ensuing sulfide anion 1,3‐alkynone and a nucleophilic aromatic substitution rearomatization cascade give S ‐heterocyclic product in yields 41–99 %.

Language: Английский

Citations

2

Synthesis of 4-styrylquinolines via direct oxidative C3-alkenylation of anthranils under Pd(ii) catalysis DOI

Annapurna Awasthi,

Khushboo Tiwari,

Pushpendra Yadav

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(15), P. 2054 - 2057

Published: Jan. 1, 2024

The palladium-catalyzed oxidative C3-alkenylation of anthranils (2,1-benzisoxazoles) with various styrenes has been successfully achieved.

Language: Английский

Citations

1

Copper/Zinc-Catalyzed Stitching of 2-Carbonylanilines with Bis(ynamides): Access to Pyrrolo[2,3-b]quinolines and Its Photophysical Studies DOI
Shivani Choudhary,

Gayyur,

Arnab Mandal

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(9), P. 6274 - 6280

Published: April 20, 2024

Herein, a one-pot desulfonylative protocol enabled by copper(II)/zinc(II) salts to access pyrrolo[2,3-b]quinolines in good excellent yields from 2-carbonylanilines and ynamide-derived buta-1,3-diynes has been reported. Significantly, various carrying reactive functional groups are well tolerated. Moreover, gram-scale synthesis synthetic application highlight the practical utility of current protocol. Notably, fluorescence properties have recorded, their potential use as fluorescent probe imaging live cells demonstrated.

Language: Английский

Citations

1