Regio- and stereoselective access to highly substituted vinylphosphine oxides via metal-free electrophilic phosphonoiodination of alkynes DOI Creative Commons

Bingbing Dong,

Fengqian Zhao,

Wen‐Xin Lv

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: June 25, 2024

Abstract In general, the P-centered ring-opening of quaternary phosphirenium salts (QPrS) predominantly leads to hydrophosphorylated products, while C-centered is primarily confined intramolecular nucleophilic reactions, resulting in formation phosphorus-containing cyclization products instead difunctionalized generated through intermolecular processes. Here, promotion three-member rings by iodine anions and quenching electronegative carbon atoms cations, we successfully synthesize β -functionalized vinylphosphine oxides P-addition QPrS intermediates situ. Multiple β- iodo-substituted can be obtained with exceptional regio- stereo-selectivity reacting secondary phosphine unactivated alkynes. addition, a variety converted from C-I bonds, especially rapid construction benzo[ b ]phospholes oxides, demonstrates significance this strategy.

Language: Английский

Enantioselective Three-Component Fluoroalkylarylation of Unactivated Olefins through Nickel-Catalyzed Cross-Electrophile Coupling DOI
Hai‐Yong Tu, Fang Wang,

Liping Huo

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(21), P. 9604 - 9611

Published: May 11, 2020

A nickel-catalyzed, enantioselective, three-component fluoroalkylarylation of unactivated alkenes with aryl halides and perfluoroalkyl iodides has been described. This cross-electrophile coupling protocol utilizes a chiral nickel/BiOx system as well pendant chelating group to facilitate the challenging three-component, asymmetric difunctionalization alkenes, providing direct access valuable β-fluoroalkyl arylalkanes high efficiency excellent enantioselectivity. The mild conditions allow for broad substrate scope good functional toleration.

Language: Английский

Citations

245
Phosphorus-Based Catalysis DOI Creative Commons
Changmin Xie, Andrew J. Smaligo,

Xian-Rong Song

et al.

ACS Central Science, Journal Year: 2021, Volume and Issue: 7(4), P. 536 - 558

Published: March 16, 2021

Phosphorus-based organocatalysis encompasses several subfields that have undergone rapid growth in recent years. This Outlook gives an overview of its various aspects. In particular, we highlight key advances three topics: nucleophilic phosphine catalysis, organophosphorus catalysis to bypass oxide waste, and compound-mediated single electron transfer processes. We briefly summarize five additional chiral phosphoric acid Lewis base iminophosphorane super phosphonium salt phase frustrated pair catalysis. Although it is not catalytic nature, also discuss novel discoveries are emerging phosphorus(V) ligand coupling. conclude with some ideas about the future

Language: Английский

Citations

243
Synthetic reactions driven by electron-donor–acceptor (EDA) complexes DOI Creative Commons

Zhonglie Yang,

Yutong Liu, Kun Cao

et al.

Beilstein Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 17, P. 771 - 799

Published: April 6, 2021

The reversible, weak ground-state aggregate formed by dipole–dipole interactions between an electron donor and acceptor is referred to as electron-donor–acceptor (EDA) complex. Generally, upon light irradiation, the EDA complex turns into excited state, causing transfer give radicals initiate subsequent reactions. Besides external energy source, reactions involving participation of complexes are mild, obviating transition metal catalysts or photosensitizers in majority cases line with theme green chemistry. This review discusses synthetic concerned well mechanisms that have been shown over past five years.

Language: Английский

Citations

132
Progress in Photoinduced Radical Reactions using Electron Donor‐Acceptor Complexes DOI
Lvyin Zheng,

Liuhuan Cai,

Kailiang Tao

et al.

Asian Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 10(4), P. 711 - 748

Published: Feb. 11, 2021

Abstract Photocatalyzed organic synthesis transformation is a remarkable green synthetic strategy because of the advantages operational simplicity, high chemoselectivities, cheap, and environmental benignancy, along with extensive applications in fields organic, pharmaceutical functional material chemistry. Generally, photoredox catalysts or photosensitizers are necessary for generation their excited states to perform successive oxidative reductive reactions through single electron transfer (SET) energy (ET) process. Furthermore, exploration colored donor‐acceptor (EDA) complex charge (CT) between an electron‐rich electron‐poor substrate provides chance deliver intermediate under irradiation light, resulting formation radical activate species induce various reactions. These were performed without need any external photocatalysts mild reaction conditions. Herein, this review focuses on recent progress photoinduced addition reactions, borylations, radical‐radical cross‐coupling degradation cascade cyclization via EDA complexes. We highlight these novel methodologies applications, as well mechanisms. This will help provide references medicinal chemists who charmed by photochemical transformations based

Language: Английский

Citations

110
Shining light on halogen-bonding complexes: a catalyst-free activation mode of carbon–halogen bonds for the generation of carbon-centered radicals DOI Creative Commons
Helena F. Piedra, Carlos Valdés, Manuel Plaza

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(21), P. 5545 - 5568

Published: Jan. 1, 2023

This review provides a comprehensive overview on examples of how photochemical excitation halogen-bonding complexes can be useful for the generation carbon-centered radicals and their participation in synthetic organic transformations.

Language: Английский

Citations

46
A general and green fluoroalkylation reaction promoted via noncovalent interactions between acetone and fluoroalkyl iodides DOI
Ting Mao,

Ming-Jian Ma,

Liang Zhao

et al.

Chemical Communications, Journal Year: 2020, Volume and Issue: 56(12), P. 1815 - 1818

Published: Jan. 1, 2020

The first example of visible light promoted fluoroalkylation reactions initiated via noncovalent interactions between acetone and fluoroalkyl iodides is presented. reaction system features synthetic simplicity, mild conditions without any photoredox catalyst, high functional group tolerance. A wide range substrate scopes such as alkenes, alkynes (hetero)arenes were all compatible with the system.

Language: Английский

Citations

82
Radical Perfluoroalkylation of Aliphatic Substrates DOI
Damian E. Yerien, Sebastián Barata‐Vallejo, Al Postigo

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(12), P. 7756 - 7794

Published: May 25, 2023

A selection of perfluoroalkylation reactions aliphatic substrates that display methodological and synthetic amplitude will be studied, giving examples their applications mechanistic details. An array approaches for fluoroalkylation are documented; in particular, radical protocols prominent among methods. To effect, addition perfluoroalkyl radicals RF (RF=CnF2n+1, n > 1) to unsaturated organic serve as one the most direct efficacious ways access fluoroalkylated scaffolds. The syntheses perfluoroalkyl-substituted vinyl, alkynyl, allylic compounds; hydro-, iodo-, oxy-perfluoroalkylated alkanes olefins; carbonyl enamides, amides, thioamides, hydrazones; multicomponent studied. While there a number accomplished reports on organofluorination, we aim provide an overview radical-involved substrates, covering from 2018 early 2023, summarized Tables 1–4.

Language: Английский

Citations

41
Expanding Reaction Profile of Allyl Carboxylates via 1,2-Radical Migration (RaM): Visible-Light-Induced Phosphine-Catalyzed 1,3-Carbobromination of Allyl Carboxylates DOI
Gaoyuan Zhao, Sang-Hyun Lim, Djamaladdin G. Musaev

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(15), P. 8275 - 8284

Published: April 5, 2023

Allyl carboxylates are useful synthetic intermediates in a variety of organic transformations, including catalytic nucleophilic/electrophilic allylic substitution reactions and 1,2-difunctionalization reactions. However, the 1,3-difunctionalization allyl remains elusive. Herein, we report first photoinduced, phosphine-catalyzed 1,3-carbobromination carboxylates, affording range valuable substituted isopropyl (sIPC). The transformation has broad functional group tolerance, is amenable to late-stage modification complex molecules gram-scale synthesis, expands reaction profiles phosphine catalysis. Preliminary experimental computational studies suggest non-chain-radical mechanism involving formation an electron donor-acceptor complex, 1,2-radical migration (RaM), Br-atom transfer processes. We anticipate that 1,2-RaM reactivity radical will both serve as platform for development new transformations synthesis.

Language: Английский

Citations

32
Phenanthroline-Initiated Anti-selective Hydrosulfonylation of Unactivated Alkynes with Sulfonyl Chlorides DOI

Ci-Shuang Dong,

Wen‐Yan Tong,

Peng Ye

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(10), P. 6983 - 6993

Published: May 8, 2023

A simple and general method for anti-selective hydrosulfonylation of unactivated alkynes with sulfonyl chlorides in the presence a catalytic amount phenanthroline-based Lewis base (Me3Si)3SiH as hydrogen atom donor has been developed. The protocol proceeds efficiently under mild metal-free conditions, delivering diverse set (Z)-vinyl sulfones high stereoselectivity. Additionally, displays excellent functional-group compatibility can be applied to late-stage modifications complex drugs their derivatives. Experimental density functional theory studies unveiled that key transformation's success is employment base, which interacts form halogen-bond accelerates cleavage S–Cl bonds irradiation visible light.

Language: Английский

Citations

27
Photochemical Synthesis of Lactones, Cyclopropanes and ATRA Products: Revealing the Role of Sodium Ascorbate** DOI Creative Commons

Marie Rrapi,

Charikleia S. Batsika,

Nikolaos F. Nikitas

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Feb. 7, 2024

Abstract Light‐mediated processes have received significant attention, since they re‐surfaced unconventional reactivity platforms, complementary to conventional polar chemistry. γ‐Lactones and cyclopropanes are prevalent moieties, found in numerous natural products pharmaceuticals. Among various methods for their synthesis, light‐mediated protocols coming the spotlight, although these contingent upon use of photoorgano‐ or metal‐based catalysts. Herein, we introduce a novel photochemical activation iodo‐reagents via cheap sodium ascorbate ascorbic acid enable homolytic scission addition onto double bonds. The developed protocol was applied successfully formal [3+2] cycloaddition synthesis γ‐lactones, traditional atom transfer radical (ATRA) reactions one‐pot two‐step conversion alkenes cyclopropanes. In all cases, desired were obtained good high yields, while reaction mechanism thoroughly investigated. Depending on nature iodo‐reagent, halogen hydrogen‐bonded complex is formed, which initiates process.

Language: Английский

Citations

13