Photoinduced Selective B–H Activation of nido-Carboranes DOI

Sheng‐Wen Xu,

Hongjian Zhang, Jingkai Xu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7791 - 7802

Published: March 10, 2024

The development of new synthetic methods for B–H bond activation has been an important research area in boron cluster chemistry, which may provide opportunities to broaden the application scope clusters. Herein, we present a reaction strategy direct site-selective functionalization nido-carboranes initiated by photoinduced cage via noncovalent cage···π interaction. As result, nido-carborane radical is generated through single electron transfer from 3D 2D photocatalyst upon irradiation with green light. resulting transient could be directly probed advanced time-resolved EPR technique. In air, subsequent transformations active have led efficient and selective B–N, B–S, B–Se couplings presence N-heterocycles, imines, thioethers, thioamides, selenium ethers. This protocol also facilitates both late-stage modification drugs synthesis nido-carborane-based drug candidates neutron capture therapy (BNCT).

Language: Английский

Metal-catalyzed asymmetric reactions enabled by organic peroxides DOI

Nengbo Zhu,

Huijie Yao,

Xiyu Zhang

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(5), P. 2326 - 2349

Published: Jan. 1, 2024

This review summarizes the advances in metal-catalyzed asymmetric reactions enabled by organic peroxides that have been found to exhibit multifunctionalities, for instance, applied as stoichiometric reactants, reagents, or catalytic amount reagents.

Language: Английский

Citations

18
Desymmetrization–Addition Reaction of Cyclopropenes to Imines via Synergistic Photoredox and Cobalt Catalysis DOI

Xiang‐Kui He,

Liang‐Qiu Lu,

Bao-Ru Yuan

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 18892 - 18898

Published: July 5, 2024

Herein, we designed a reaction for the desymmetrization-addition of cyclopropenes to imines by leveraging synergy between photoredox and asymmetric cobalt catalysis. This protocol facilitated synthesis series chiral functionalized cyclopropanes with high yield, enantioselectivity, diastereoselectivity (44 examples, up 93% yield >99% ee). A possible mechanism involving cyclopropene desymmetrization Co-H species imine addition Co-alkyl was proposed. study provides novel route important extends frontier metallaphotoredox

Language: Английский

Citations

17
Ligand-Enabled “Two-in-One” Metallaphotocatalytic Cross Couplings DOI
Jianbin Li, Ding Zhang, Zheng Hu

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1635 - 1654

Published: Jan. 15, 2025

Metallaphotoredox cross coupling (MCC) is ranking among the most advanced synthetic methodology as it can access chemical space that difficult to attain under conventional conditions. Earlier developed MCC mandates an independent transition metal catalyst and respective photocatalyst, thus constituting a dual catalytic manifold. Complementarily, paradigm-shifting metallaphotoredox strategy capitalizes on single photoreactive complex emerging, which brings not only operational simplification but also unexpected mechanistic insights. This perspective compiled recent advances in monocatalytic couplings categorized them based ligands confer distinct photoreactivities various mechanisms. To this end, ligand-enabled oxidative addition, transmetalation, reductive elimination other radical-involving pathways were summarized with notable examples. In way, we wish provide handy guideline for readers who are interested emerging field inspire more future endeavors MCCs beyond.

Language: Английский

Citations

3
Photoredox/Cr-catalyzed enantioselective radical-polar crossover transformation via C-H functionalization DOI Creative Commons
Siyuan Tang,

Z. Z. Wang,

Ao Yu

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Feb. 4, 2025

Asymmetric multicomponent reactions that aim to control multiple chiral centers with high selectivity in a single step remain an on-gonging challenge. The realm of enantioselective radical-polar crossover transformation achieved through C-H Functionalization has yet be fully explored. Herein, we present successful description photoredox/Cr-catalyzed three-component (hetero)arylalkylation 1,3-dienes functionalization. A diverse array homoallylic alcohols could obtained good excellent yields, accompanied by outstanding enantioselectivity. asymmetric build two simultaneously and demonstrates broad substrate tolerance, accommodating various drug-derived aldehydes, (hetero)aromatics, 1,3-diene derivatives. Preliminary mechanistic studies indicate the involvement radical intermediate, allylic chromium species reacting aliphatic aromatic aldehydes Zimmerman–Traxler transition states enabled dual photoredox catalysis. ongoing Here, authors photoredox- chromium-catalyzed

Language: Английский

Citations

2
Asymmetric 1,4-functionalization of 1,3-enynes via dual photoredox and chromium catalysis DOI Creative Commons
Feng‐Hua Zhang,

Xiaochong Guo,

Xianrong Zeng

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Aug. 26, 2022

Abstract The merger of photoredox and transition-metal catalysis has evolved as a robust platform in organic synthesis over the past decade. stereoselective 1,4-functionalization 1,3-enynes, prevalent synthon synthetic chemistry, could afford valuable chiral allene derivatives. However, tremendous efforts have been focused on ionic reaction pathway. radical-involved asymmetric 1,3-enynes remains prominent challenge. Herein, we describe three-component 1,4-dialkylation via dual chromium to provide allenols. This method features readily available starting materials, broad substrate scope, good functional group compatibility, high regioselectivity, simultaneous control axial central chiralities. Mechanistic studies suggest that this proceeds through redox-neutral

Language: Английский

Citations

67
Three-component carboacylation of alkenes via cooperative nickelaphotoredox catalysis DOI Creative Commons
Dingyi Wang, Lutz Ackermann

Chemical Science, Journal Year: 2022, Volume and Issue: 13(24), P. 7256 - 7263

Published: Jan. 1, 2022

Various commercially available acyl chlorides, aldehydes, and alkanes were exploited for versatile three-component 1,2-carboacylations of alkenes to forge two vicinal C-C bonds through the cooperative action nickel sodium decatungstate catalysis. A wealth ketones with high levels structural complexity was rapidly obtained via direct functionalization C(sp2)/C(sp3)-H in a modular manner. Furthermore, regioselective late-stage modification natural products showcased practical utility strategy, generally featuring resource economy ample substrate scope.

Language: Английский

Citations

50
Photoredox-Catalyzed and Copper(II) Salt-Assisted Radical Addition/Hydroxylation Reaction of Alkenes, Sulfur Ylides, and Water DOI
Dongmei Yan,

Shuang-Hua Xu,

Hao Qian

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(6), P. 3279 - 3285

Published: Feb. 25, 2022

A visible light-driven photoredox-catalyzed and copper(II)-assisted three-component radical addition/hydroxylation reaction of alkenes, sulfur ylides, water is reported. This process shows broad substrate scope high functional group tolerance, with respect to both readily available ylides providing high-yielding practical access valuable γ-hydroxy carbonyl compounds. Key the success controlled generation α-carbonyl carbon radicals from via sulfonium salts by a visible-light-driven proton-coupled electron transfer (PCET) strategy in mixture 2,2,2-trifluoroethanol/CH2Cl2. Addition Cu(TFA)2·H2O helps accelerate radical-cation crossover improve efficiency. Mechanistic studies suggest that hydroxy moiety products stems water. study also builds up platform for further investigation into synthetic chemistry ylides.

Language: Английский

Citations

49
Visible-light-induced metal-free coupling of C(sp3)–H sources with heteroarenes DOI

Anogh Ghosh,

Pranjal Pyne, Sumit Ghosh

et al.

Green Chemistry, Journal Year: 2022, Volume and Issue: 24(8), P. 3056 - 3080

Published: Jan. 1, 2022

This critical review chronologically summarizes the metal-free coupling methodologies of C(sp 3 )–H sources with heteroarenes induced by visible light. The articles which are published up to January 2022 on this topic enclosed here.

Language: Английский

Citations

46
Two-in-one metallaphotoredox cross-couplings enabled by a photoactive ligand DOI Creative Commons
Jianbin Li, Chia‐Yu Huang, Chao‐Jun Li

et al.

Chem, Journal Year: 2022, Volume and Issue: 8(9), P. 2419 - 2431

Published: June 9, 2022

Language: Английский

Citations

41
Recent Advances in Visible-Light Photoredox Catalysis for the Thiol-Ene/Yne Reactions DOI Creative Commons
Qian Xiao, Qing‐Xiao Tong, Jian‐Ji Zhong

et al.

Molecules, Journal Year: 2022, Volume and Issue: 27(3), P. 619 - 619

Published: Jan. 18, 2022

Visible-light photoredox catalysis has been established as a popular and powerful tool for organic transformations owing to its inherent characterization of environmental friendliness sustainability in the past decades. The thiol-ene/yne reactions, direct hydrothiolation alkenes/alkynes with thiols, represents one most efficient atom-economic approaches carbon-sulfur bonds construction. In traditional methodologies, harsh conditions such stoichiometric reagents or specialized UV photo-apparatus were necessary suffering from various disadvantages. particular, visible-light also demonstrated be greener milder protocol reactions recent years. Additionally, unprecedented advancements have achieved this area during decade. review, we will summarize advances catalyzed 2015 2021. Synthetic strategies, substrate scope, proposed reaction pathways are mainly discussed.

Language: Английский

Citations

40