Enantioselective catalytic radical decarbonylative azidation and cyanation of aldehydes DOI Creative Commons
Rui Wang, Chengyu Wang, Peng Liu

et al.

Science Advances, Journal Year: 2023, Volume and Issue: 9(35)

Published: Sept. 1, 2023

Empowered by the ubiquity of carbonyl functional groups in organic compounds, decarbonylative functionalization was prevalent construction complex molecules. Under this context, asymmetric has emerged as an efficient pathway to accessing chiral motifs. However, ablation enantiomeric control a conventional 2e transition metal–catalyzed process notable because harsh conditions (high temperatures, etc.) that are usually required. To address challenge and use readily accessible aldehyde directly, we report radical azidation cyanation. Diverse aldehydes were directly used alkyl precursor, engaging subsequent inner-sphere or outer-sphere ligand transfer where motifs (CN N 3 ) could be incorporated excellent site- enantioselectivity. Mild conditions, broad scope, regioselectivity (driven polarity-matching strategy), enantioselectivity shown for both transformations. This strategy using precursor offered powerful reaction manifold transformations construct regio- stereoselectively.

Language: Английский

Site- and enantioselective cross-coupling of saturated N-heterocycles with carboxylic acids by cooperative Ni/photoredox catalysis DOI Creative Commons
Xiaomin Shu,

De Zhong,

Qian Huang

et al.

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

Published: Jan. 9, 2023

Abstract Site- and enantioselective cross-coupling of saturated N -heterocycles carboxylic acids—two the most abundant versatile functionalities—to form pharmaceutically relevant α-acylated amine derivatives remains a major challenge in organic synthesis. Here, we report general strategy for highly site- α-acylation with situ-activated acids. This modular approach exploits hydrogen-atom-transfer reactivity photocatalytically generated chlorine radicals combination asymmetric nickel catalysis to selectively functionalize cyclic α-amino C−H bonds presence benzylic, allylic, acyclic α-amino, α-oxy methylene groups. The mild scalable protocol requires no organometallic reagents, displays excellent chemo-, enantioselectivity, is amenable late-stage diversification, including synthesis previously inaccessible Taxol derivatives. Mechanistic studies highlight exceptional versatility chiral catalyst orchestrating (i) catalytic elimination, (ii) alkyl radical capture, (iii) cross-coupling, (iv) induction.

Language: Английский

Citations

58
Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents DOI Creative Commons
Akira Yoshimura, Viktor V. Zhdankin

Chemical Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 13, 2024

Hypervalent iodine(III) compounds have found wide application in modern organic chemistry as environmentally friendly reagents and catalysts. iodine are commonly used synthetically important halogenations, oxidations, aminations, heterocyclizations, various oxidative functionalizations of substrates. Iodonium salts arylating reagents, while iodonium ylides imides excellent carbene nitrene precursors. Various derivatives benziodoxoles, such azidobenziodoxoles, trifluoromethylbenziodoxoles, alkynylbenziodoxoles, alkenylbenziodoxoles group transfer the presence transition metal catalysts, under metal-free conditions, or using photocatalysts photoirradiation conditions. Development hypervalent catalytic systems discovery highly enantioselective reactions chiral represent a particularly recent achievement field chemistry. Chemical transformations promoted by many cases unique cannot be performed any other common, non-iodine-based reagent. This review covers literature published mainly last 7-8 years, between 2016 2024.

Language: Английский

Citations

33
Enantioselective Intermolecular Radical Amidation and Amination of Benzylic C−H Bonds via Dual Copper and Photocatalysis DOI Creative Commons
Xuemeng Chen, Zhong Lian, Søren Kramer

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(13)

Published: Feb. 1, 2023

A method for direct access to enantioenriched benzylic amides and carbamate-protected primary benzylamines by C-H functionalization is reported. The substrate used as limiting reagent with only a small excess of the unactivated amide or carbamate nucleophile. enantioselective intermolecular dehydrogenative C-N bond formation enabled combination chiral copper catalyst, photocatalyst, an oxidant, it takes place under mild conditions, which allow broad scope. compatible late-stage functionalization, provides easy 15 N-labeled amines starting from cheap NH4 Cl.

Language: Английский

Citations

33
Intermolecular Enantioselective Benzylic C(sp3)−H Amination by Cationic Copper Catalysis** DOI

Ling Dai,

Yingying Chen, Li‐Jun Xiao

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(24)

Published: April 14, 2023

Chiral benzylic amines are privileged motifs in pharmacologically active molecules. Intramolecular enantioselective radical C(sp3 )-H functionalization by hydrogen-atom transfer has emerged as a straightforward, powerful tool for the synthesis of chiral amines, but methods intermolecular amination remain elusive. Herein, we report cationic copper catalytic system with peroxide an oxidant. This mild, straightforward method can be used to transform array feedstock alkylarenes and amides into high enantioselectivities, it good functional group tolerance broad substrate scope. More importantly, synthesize bioactive molecules, including drugs. Preliminary mechanistic studies indicate that reaction involves radicals generated transfer.

Language: Английский

Citations

31
Asymmetric Three-Component Radical Alkene Carboazidation by Direct Activation of Aliphatic C–H Bonds DOI
Liang Ge,

Hongkai Wang,

Yangbin Liu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(19), P. 13347 - 13355

Published: May 6, 2024

Azide compounds are widely present in natural products and drug molecules, their easy-to-transform characteristics make them used the field of organic synthesis. The merging transition-metal catalysis with radical chemistry offers a versatile platform for carboazidation alkenes, allowing rapid assembly highly functionalized azides. However, direct use readily available hydrocarbon feedstocks as sp

Language: Английский

Citations

16
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

Citations

16
Manganese-Catalyzed Electrochemical Oxidation of Tryptophan-Containing Peptides and Indole Derivatives by O2 DOI
Min Xu, Qin He, Xiaojiang Li

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 3928 - 3939

Published: Feb. 20, 2025

Language: Английский

Citations

2
Bioinspired Copper/Amine Cooperative Catalysis Enables Asymmetric Radical Azidation DOI
Rui Wang, Yujie Liang,

Kang‐Jie Bian

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 12, 2025

Asymmetric radical transformations (ARTs) are vital for constructing chiral drugs and materials, while the highly reactive nature of radicals often imposes a challenge in selectivity control these processes. Inspired by principles enzyme-cofactor cooperation to enhance stereochemical induction enantioselective transformations, we developed an asymmetric azidation via cooperative organo- transition metal catalysis. This approach enables efficient synthesis heavily functionalized tertiary azides from readily available aldehydes. The key this process is use both organocatalysts transiently convert aldehydes corresponding cationic species upon oxidation along with detailed screening metal-azide catalysts cooperatively stereoinduction carbon-azide bond formation. DFT studies suggest favorable stereocontrol model validate crucial roles chirality pairing catalytic schemes. We envision that copper/amine catalysis could offer useful strategy tetrasubstituted stereogenic carbon transformation development.

Language: Английский

Citations

1
Mechanisms of C(sp3)–H and C=C selective oxidative heterofunctionalizations by non-heme Fe and Mn mimics of oxygenase enzymes DOI
Konstantin P. Bryliakov

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 508, P. 215793 - 215793

Published: March 18, 2024

Language: Английский

Citations

9
Simple, catalytic C(sp3)–H azidation using the C–H donor as the limiting reagent DOI

James F. Hooson,

Hai N. Tran,

Kang‐Jie Bian

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(27), P. 3705 - 3708

Published: Jan. 1, 2024

C(sp 3 )–H bonds can be directly azidated using simple iron and manganese catalysts commercial Selectfluor TMSN as reagents.

Language: Английский

Citations

7