Strategies and Mechanisms of First-Row Transition Metal-Regulated Radical C–H Functionalization DOI
Xinghua Wang,

J. P. He,

Yanan Wang

et al.

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(17), P. 10192 - 10280

Published: Aug. 8, 2024

Radical C–H functionalization represents a useful means of streamlining synthetic routes by avoiding substrate preactivation and allowing access to target molecules in fewer steps. The first-row transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu) are Earth-abundant can be employed regulate radical functionalization. use such is desirable because the diverse interaction modes between metal complexes species including addition center, ligand complexes, substitution single-electron transfer radicals hydrogen atom noncovalent complexes. Such interactions could improve reactivity, diversity, selectivity transformations allow for more challenging reactions. This review examines achievements this promising area over past decade, with focus on state-of-the-art while also discussing existing limitations enormous potential high-value regulated these metals. aim provide reader detailed account strategies mechanisms associated

Language: Английский

A light-driven enzymatic enantioselective radical acylation DOI
Yuanyuan Xu, Hongwei Chen, Lu Yu

et al.

Nature, Journal Year: 2023, Volume and Issue: 625(7993), P. 74 - 78

Published: Dec. 18, 2023

Language: Английский

Citations

67
Recent advances in combining photo- and N-heterocyclic carbene catalysis DOI Creative Commons
Xiaochen Wang,

Senhui Wu,

Rongxin Yang

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(46), P. 13367 - 13383

Published: Jan. 1, 2023

This review summarizes recent advances in combining photo- and N-heterocyclic carbene catalysis, as well provides an outlook on future opportunities challenges.

Language: Английский

Citations

43
Radical Reactions with N-Heterocyclic Carbene (NHC)-Derived Acyl Azoliums for Access to Multifunctionalized Ketones DOI

Hui Cai,

Xiaoqun Yang,

Shi‐Chao Ren

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8270 - 8293

Published: May 13, 2024

As one of the most important key intermediates, NHC-bound acylazolium-based ionic transformations have been intensively explored in past two decades. With expeditious development NHC-catalyzed radical recent years, acylazolium chemistry has reached another level, with number relevant publications increasing significantly. However, a summary focused on acylations NHC-derived acyl azoliums classified according to mechanistic difference not reported. Such detailed classification and deep analysis provide opportunities for better understanding history trend this field. In review, reactions N-heterocyclic carbene (NHC)-derived are systematically introduced. The achievements challenges within area also summarized discussed at end.

Language: Английский

Citations

23
Remote site-selective arene C–H functionalization enabled by N-heterocyclic carbene organocatalysis DOI
Qing‐Zhu Li,

Wen‐Lin Zou,

Zhaoyuan Yu

et al.

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(8), P. 900 - 911

Published: July 11, 2024

Language: Английский

Citations

17
Diastereoselective Radical Aminoacylation of Olefins through N-Heterocyclic Carbene Catalysis DOI

Wen-Deng Liu,

Woojin Lee,

Hanyu Shu

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(49), P. 22767 - 22777

Published: Nov. 24, 2022

There have been significant advancements in radical-mediated reactions through covalent-based organocatalysis. Here, we present the generation of iminyl and amidyl radicals via N-heterocyclic carbene (NHC) catalysis, enabling diastereoselective aminoacylation trisubstituted alkenes. Different from photoredox single electron transfer deprotonated Breslow intermediate to O-aryl hydroxylamine generates an NHC-bound ketyl radical, which undergoes diastereocontrolled cross-coupling with prochiral C-centered radical. This operationally simple method provides a straightforward access variety pyrroline oxazolidinone heterocycles vicinal stereocenters (77 examples, up >19:1 d.r.). Electrochemical studies acyl thiazolium salts support our reaction design highlight reducing ability Breslow-type derivatives. A detailed computational analysis this organocatalytic system suggests that radical–radical coupling is rate-determining step, π–π stacking interaction between radical intermediates subtly controls diastereoselectivity.

Language: Английский

Citations

56
Branched-Selective Hydroacylation of Alkenes via Photoredox Cobalt and N-Heterocyclic Carbene Cooperative Triple Catalysis DOI
Xiangzhang Tao, Qing Wang, Lingyu Kong

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(24), P. 15241 - 15248

Published: Nov. 29, 2022

A Markovnikov-selective hydroacylation of alkenes has been achieved via the synergistic merger cobalt, photoredox and N-heterocyclic carbene catalysis. The closely incorporated catalytic cycles allow for Co(III) generation by photochemical oxidation instead chemical oxidants or anodizing process. This mild, operationally simple protocol converts a wide variety commercially available aroyl fluorides into corresponding ketones in high yield with branched selectivity.

Language: Английский

Citations

42
The green chemistry paradigm in modern organic synthesis DOI
Sergei G. Zlotin, Ksenia S. Egorova, Valentine P. Ananikov

et al.

Russian Chemical Reviews, Journal Year: 2023, Volume and Issue: 92(12), P. RCR5104 - RCR5104

Published: Dec. 1, 2023

After the appearance of green chemistry concept, which was introduced in vocabulary early 1990s, its main statements have been continuously developed and modified. Currently, there are 10–12 cornerstones that should form basis for an ideal chemical process. This review analyzes accumulated experience achievements towards design products processes reduce or eliminate use generation hazardous substances. The presents views leading Russian scientists specializing various fields this subject, including homogeneous heterogeneous catalysis, fine basic organic synthesis, electrochemistry, polymer chemistry, based on bio-renewable feedstocks energetic compounds materials. A new approach to quantitative evaluation environmental friendliness by authors is described. <br> bibliography includes 1761.

Language: Английский

Citations

39
Regiodivergent C−H Acylation of Arenes by Switching from Ionic‐ to Radical‐Type Chemistry Using NHC Catalysis DOI

Jannik Reimler,

Xiaoye Yu,

Nico Spreckelmeyer

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(27)

Published: April 24, 2023

The Friedel-Crafts acylation reaction, which belongs to the class of electrophilic aromatic substitutions is a highly valuable and versatile reaction in synthesis. Regioselectivity predictable determined by electronic as well steric factors (hetero)arene substrate. Herein, radical approach for arenes heteroarenes presented. C-H achieved through mild cooperative photoredox/NHC catalysis with cross-coupling an arene cation NHC-bound ketyl key step. As compared classical acylation, regiodivergent outcome observed upon switching from ionic mode. In these divergent reactions, aroyl fluorides act reagents both process.

Language: Английский

Citations

34
Direct allylic acylation via cross-coupling involving cooperative N‑heterocyclic carbene, hydrogen atom transfer, and photoredox catalysis DOI Creative Commons
Xiaochen Wang,

Rongxin Yang,

Binbing Zhu

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: May 23, 2023

Herein, we report a mild, operationally simple, multicatalytic method for the synthesis of β,γ-unsaturated ketones via allylic acylation alkenes. Specifically, combines N‑heterocyclic carbene catalysis, hydrogen atom transfer and photoredox catalysis cross-coupling reactions between wide range feedstock carboxylic acids readily available olefins to afford structurally diverse without olefin transposition. The could be used install acyl groups on highly functionalized natural-product-derived compounds with no need substrate pre-activation, C-H functionalization proceed excellent site selectivity. To demonstrate potential applications method, convert representative coupling product into various useful synthons.

Language: Английский

Citations

33
Photoinduced Electron Transfer from Xanthates to Acyl Azoliums: Divergent Ketone Synthesis via N‐Heterocyclic Carbene Catalysis DOI
Chang‐Yin Tan, Minseok Kim, Sungwoo Hong

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(32)

Published: June 12, 2023

Considering the prevalence of alcohols and carboxylic acids, their fragment cross-coupling reactions could hold significant implications in organic synthesis. Herein, we report a versatile method for synthesizing diverse range ketones from acid derivatives via N-heterocyclic carbene (NHC) catalysis. Mechanistic investigations revealed that photoexcited xanthates acyl azoliums undergo single electron transfer (SET) under photocatalyst-free conditions, generating NHC-derived ketyl radicals alkyl radicals. These open-shell intermediates subsequently radical-radical reaction, yielding valuable ketones. Furthermore, this approach can be employed three-component involving alkenes enynes, resulting structurally cross-coupled The unified strategy offers unique opportunity coupling derivatives, accommodating functional groups even complex settings.

Language: Английский

Citations

33