Carbene Formation or Reduction of the Diazo Functional Group? An Unexpected Solvent‐Dependent Reactivity of Cyclic Diazo Imides DOI Creative Commons
Yaseen Hussain, Claire Empel, René M. Koenigs

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(40)

Published: July 28, 2023

Abstract The control of the reactivity diazo compounds is commonly achieved by choice a suitable catalyst, e.g. via stabilization singlet carbenes or radical intermediates. Herein, we report on light‐promoted cyclic imides with thiols, where solvent results in two fundamentally different reaction pathways. In dichloromethane (DCM), carbene formed initially and engages cascade C−H functionalization/thiolation to deliver indane‐fused pyrrolidines good excellent yields. When switching acetonitrile solvent, pathway shut down an unusual reduction compound occurs under otherwise identical conditions, aryl thiol acts as reductant. A combined set experimental computational studies was carried out obtain mechanistic understanding support that indane formation proceeds insertion triplet carbene, while electron transfer process.

Language: Английский

Visible Light-Induced Reactions of Diazo Compounds and Their Precursors DOI
Ziyan Zhang, Vladimir Gevorgyan

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(11), P. 7214 - 7261

Published: May 16, 2024

In recent years, visible light-induced reactions of diazo compounds have attracted increasing attention in organic synthesis, leading to improvement existing reactions, as well the discovery unprecedented transformations. Thus, photochemical or photocatalytic generation both carbenes and radicals provide milder tools toward these key intermediates for many valuable However, vast majority transformations represent new reactivity modes compounds, which are achieved by decomposition photoredox catalysis. particular, use a redox-active photocatalysts opens avenue plethora radical reactions. The application methods led inaccessible classical associated with metal carbenes. most cases, act sources but can also serve acceptors. Importantly, described processes operate under mild, practical conditions. This Review describes this subfield compound chemistry, particularly focusing on advancements.

Language: Английский

Citations

59
Visible photons as ideal reagents for the activation of coloured organic compounds DOI Creative Commons
Lorenzo Di Terlizzi, Luca Nicchio,

Stefano Protti

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(10), P. 4926 - 4975

Published: Jan. 1, 2024

In search for the perfect wave(length). This review is dedicated to recent efforts in development of visible light driven photochemical strategies occurring coloured organic compounds.

Language: Английский

Citations

11
Carbene Formation or Reduction of the Diazo Functional Group? An Unexpected Solvent‐Dependent Reactivity of Cyclic Diazo Imides DOI Creative Commons
Yaseen Hussain, Claire Empel, René M. Koenigs

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(40)

Published: July 28, 2023

The control of the reactivity diazo compounds is commonly achieved by choice a suitable catalyst, e.g. via stabilization singlet carbenes or radical intermediates. Herein, we report on light-promoted cyclic imides with thiols, where solvent results in two fundamentally different reaction pathways. In dichloromethane (DCM), carbene formed initially and engages cascade C-H functionalization/thiolation to deliver indane-fused pyrrolidines good excellent yields. When switching acetonitrile solvent, pathway shut down an unusual reduction compound occurs under otherwise identical conditions, aryl thiol acts as reductant. A combined set experimental computational studies was carried out obtain mechanistic understanding support that indane formation proceeds insertion triplet carbene, while electron transfer process.

Language: Английский

Citations

14
Photochemical multicomponent transformation of acceptor-only diazoalkanes by merging their cycloaddition and carbene reactivities DOI
Bao‐Gui Cai, Guoyong Xu, Jun Xuan

et al.

Chinese Chemical Letters, Journal Year: 2023, Volume and Issue: 34(9), P. 108335 - 108335

Published: March 15, 2023

Language: Английский

Citations

13
Dioxane promoted photochemical O-alkylation of 1,3-dicarbonyl compounds beyond carbene insertion into C–H and C–C bonds DOI

Xinlong Zhou,

Jingjing Jiang, Min Zhang

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(32), P. 4330 - 4333

Published: Jan. 1, 2024

1,4-Dioxane promoted O -alkylation of various 1,3-dicarbonyl compounds beyond previous carbene insertion into C–H and C–C bonds has been disclosed.

Language: Английский

Citations

5
Violet-Light-Induced Ring-Opening of Anthranils with Chlorodiazirines DOI

Yikun Ren,

Chuanyang Song,

Mengna Hua

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 30, 2025

A violet-light-induced ring-opening of anthranils with chlorodiazirines has been developed. The metal-free protocol provides a rapid and efficient approach to N-(2-carbonylaryl)benzamides in moderate good yields under mild conditions. reaction appears involve α-chlorocarbenes, which trigger the anthranils.

Language: Английский

Citations

0
Regioselective Synthesis of N-Vinyl Pyrazoles from Vinyl Sulfonium Salts with Diazo Compounds DOI

Shichong Wang,

Huayan Xu, Ruoyu Zhang

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(36), P. 6746 - 6750

Published: Sept. 5, 2023

Herein, we develop a base-promoted regioselective synthesis of N-vinyl pyrazoles from vinyl sulfonium salts with diazo compounds. This metal-free synthetic protocol provides an efficient and practical approach to diverse in good excellent yields under mild conditions. The reaction appears experience [3 + 2] annulation anions rather than compounds, followed by N-vinylation.

Language: Английский

Citations

10
Photochemical “Cut and Sew” Transformations of Ethynylbenziodoxolone Reagents and Diazo Compounds DOI

Mengting Cao,

Yikun Ren,

Ruoyu Zhang

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(34), P. 6300 - 6304

Published: Aug. 23, 2023

Herein, we disclose a visible-light-induced oxy-alkynylation of diazo compounds with ethynylbenziodoxolones. The efficient protocol provides mild and metal-free methodology to synthesize propargylic esters in moderate good yields. Notably, this carbene transfer reaction appears involve an oxonium ylide intermediate, followed by intramolecular ligand exchange reductive elimination.

Language: Английский

Citations

8
Base-free regio- and stereoselective photochemical synthesis of enol ethers from 1,3-dicarbonyl compounds DOI

Keyong Zhu,

Wen-Jing Yu,

Xinlong Zhou

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(84), P. 12605 - 12608

Published: Jan. 1, 2023

A visible light-induced kinetic controlled regioselective O-alkylation of various 1,3-dicarbonyl compounds with diazoacetates and cyclic ethers has been developed. The protocol provides a green practical approach to highly stereoselective enol under mild base-free conditions in good excellent yields.

Language: Английский

Citations

3
Carbene Formation or Reduction of the Diazo Functional Group? An Unexpected Solvent‐Dependent Reactivity of Cyclic Diazo Imides DOI Creative Commons
Yaseen Hussain, Claire Empel, René M. Koenigs

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(40)

Published: July 28, 2023

Abstract The control of the reactivity diazo compounds is commonly achieved by choice a suitable catalyst, e.g. via stabilization singlet carbenes or radical intermediates. Herein, we report on light‐promoted cyclic imides with thiols, where solvent results in two fundamentally different reaction pathways. In dichloromethane (DCM), carbene formed initially and engages cascade C−H functionalization/thiolation to deliver indane‐fused pyrrolidines good excellent yields. When switching acetonitrile solvent, pathway shut down an unusual reduction compound occurs under otherwise identical conditions, aryl thiol acts as reductant. A combined set experimental computational studies was carried out obtain mechanistic understanding support that indane formation proceeds insertion triplet carbene, while electron transfer process.

Language: Английский

Citations

2