Radical Difunctionalization of Unsaturated Hydrocarbons Employing the Same Functional Reagent DOI

Wen‐Chan Tian,

Nan‐Nan Dai,

Yunpeng Lu

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(17), P. 3524 - 3541

Published: July 3, 2024

Abstract The radical difunctionalization of unsaturated hydrocarbons serves as an efficient means to rapidly construct molecular skeletons and synthesize‐highly valuable compounds. In this transformational process, diverse positions within are sequentially functionalized by a single precursor reagent, thereby achieving highly selective transformations that promote atom economy. Furthermore, approach minimizes the generation numerous byproducts stemming from cross‐coupling reactions between reactants, owing reduction number participating components. Therefore, review provides in‐depth analysis utilizing functional reagent in recent decades. discussion is based on eight different classes (carbon‐, nitrogen‐, phosphine‐, oxygen‐, sulfur‐, selenium‐, tellurium‐, chlorine‐centered radicals), emphasizing mechanism specific difunctionalization. It also analyzes detail regulation key factors such regional selectivity, unique insights into reaction transformations.

Language: Английский

Bifunctional two-carbon reagent made from acetylene via 1,2-difunctionalization and its applications DOI
Bo Yang,

Kangkui Li,

Yongdong Wang

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(3), P. 936 - 944

Published: Jan. 8, 2024

Language: Английский

Citations

6

Recent Advances in Visible Light Induced Radical 1,2-Functionalization of Alkynes DOI

Kangkui Li,

Xianyang Long,

Yue Huang

et al.

Acta Chimica Sinica, Journal Year: 2024, Volume and Issue: 82(6), P. 658 - 658

Published: Jan. 1, 2024

Language: Английский

Citations

4

Vicinal diphosphorylation of enaminones with diaryl phosphine oxides via AlCl3-mediated C N bond cleavage DOI
Xin Jin,

An Yong,

Jia Chen

et al.

Tetrahedron Letters, Journal Year: 2025, Volume and Issue: 158, P. 155472 - 155472

Published: Feb. 20, 2025

Language: Английский

Citations

0

Water-Controlled Geminal Hydroxyphosphinoylation and Diphosphinoylation of Enaminones with H-Phosphine Oxides DOI

Qiang Huang,

Xin Jin, Huabin Wang

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 6, 2025

A water-controlled geminal phosphinoylation of enaminones with H-phosphine oxides has been established through AlCl3-mediated C-N bond cleavage in this work, which provides a novel strategy for accessing various hydroxy and diphosphinoyl products 3a 4a high yields. The transformation features excellent functional group tolerance, operational simplicity, atom economy, is amenable complex molecule skeletons. Preliminary mechanism studies suggest the conversion from to involve elimination hydroxyl group, water temperature plays critical role influencing reaction pathway product selectivity. This research significant value functionalization enaminones.

Language: Английский

Citations

0

Recent progress in the catalytic transformation of acetylene DOI
Xin Yu, Shifa Zhu

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

Published: Jan. 1, 2025

Acetylene, a traditional industrial raw material, has garnered increasing attention in modern organic synthesis over the past two decades.

Language: Английский

Citations

0

Visible Light Photoredox Catalyzed Hydrophosphinylation of Unactivated Alkenes DOI
Ming Qi, An‐Wu Xu

Tetrahedron, Journal Year: 2025, Volume and Issue: unknown, P. 134712 - 134712

Published: May 1, 2025

Language: Английский

Citations

0

s-Block Metal Base-Catalyzed Synthesis of Sterically Encumbered Derivatives of Ethane-1,2-diyl-bis(diphenylphosphane oxide) (dppeO2) DOI Creative Commons
Benjamin E. Fener, Philipp Schüler,

Felix Edwin Pröhl

et al.

Organometallics, Journal Year: 2024, Volume and Issue: 43(10), P. 1095 - 1109

Published: April 24, 2024

The synthesis of ethane-1,2-diyl-bis(diarylphosphane oxides) and -phosphanes, containing bulky ortho-substituted P-bound aryl groups, poses severe challenges, such as drastic reaction conditions low yields. A potassium base-mediated hydrophosphorylation phenylacetylene with dimesitylphosphane oxide (Mes2P(O)H) yields an E/Z mixture alkenyl-dimesitylphosphane oxide. mesityl group hampers the addition a second diarylphosphane Contrary to this expected phosphane across alkyne yielding alkenylphosphane oxide, trimethylsilyl acetylene Mes2P(O)H ethane-1,2-diyl-bis(dimesitylphosphane oxide) (2b); surprisingly, TMS is substituted by hydrogen atom via rather complex mechanism. Excess TMS-C≡CH (5 equiv), ethereal solvents, soft alkali metal catalysts, large catalyst loadings 30 mol % are highly beneficial. Furthermore, at least one ortho-position must be alkylated, whereas very groups pose no obstacle. Di(n-alkyl)phosphane oxides diphenylphosphane do not show described conversion but react completely different. Alternatively, accessible metathetical approach calcium acetylide CaC2 in superbasic solvent. Reduction these (2) phosphanes (3) offers library bidentate ligands for coordination chemistry hard (e.g., Y3+) ions Pd2+).

Language: Английский

Citations

2

Modular and Diverse Synthesis of Acrylamides by Palladium‐Catalyzed Hydroaminocarbonylation of Acetylene DOI Creative Commons
Matthias Beller,

Zhusong Cao,

Qiang Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: July 10, 2024

The development of all kinds covalent drugs had a major impact on the improvement human health system. Covalent binding to target proteins is achieved by so-called electrophilic warheads, which are incorporated in respective drug molecule. In last decade, specifically acrylamides emerged as attractive warheads design. Herein, straightforward palladium-catalyzed hydroaminocarbonylation acetylene has been developed, allowing modular and diverse synthesis bio-active acrylamides. This general protocol features high atom efficiency, wide functional group compatibility, chemoselectivity proceeds additive free under mild reaction conditions. synthetic utility this showcased ibrutinib, osimertinib, other compound derivatives.

Language: Английский

Citations

2

Modular and Diverse Synthesis of Acrylamides by Palladium‐Catalyzed Hydroaminocarbonylation of Acetylene DOI Creative Commons
Matthias Beller,

Zhusong Cao,

Qiang Wang

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(40)

Published: July 10, 2024

Abstract The development of all kinds covalent drugs had a major impact on the improvement human health system. Covalent binding to target proteins is achieved by so‐called electrophilic warheads, which are incorporated in respective drug molecule. In last decade, specifically acrylamides emerged as attractive warheads design. Herein, straightforward palladium‐catalyzed hydroaminocarbonylation acetylene has been developed, allowing modular and diverse synthesis bio‐active acrylamides. This general protocol features high atom efficiency, wide functional group compatibility, chemoselectivity proceeds additive free under mild reaction conditions. synthetic utility this showcased ibrutinib, osimertinib, other compound derivatives.

Language: Английский

Citations

2

Manganese-Catalyzed Cycloalkene Ring Expansion Synthesis of Azaheterocycles DOI
Zhixin Wang, Hanxiao Xu,

Xuanzhen Han

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 2, 2024

Herein, a Mn catalytic protocol has been developed for the cycloalkene ring expansion synthesis of azaheterocycles, allowing broad-substrate-scope access to pyridine and isoquinoline derivatives. The initial monoaddition an azidyl radical alkene further as-generated C-radical addition O

Language: Английский

Citations

2