Chemical Science, Год журнала: 2021, Номер 12(46), С. 15399 - 15406
Опубликована: Янв. 1, 2021
Simple, modular assembly of complex fluoroalkyl-containing oxindole derivatives with a broad scope and excellent functional group tolerance under mild conditions (metal- photocatalyst-free). Benzyl iodides were identified as key intermediates.
Язык: Английский
Journal of the American Chemical Society, Год журнала: 2020, Номер 142(21), С. 9604 - 9611
Опубликована: Май 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.
Язык: Английский
Процитировано
243
ACS Central Science, Год журнала: 2021, Номер 7(4), С. 536 - 558
Опубликована: Март 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
Язык: Английский
Процитировано
237
Beilstein Journal of Organic Chemistry, Год журнала: 2021, Номер 17, С. 771 - 799
Опубликована: Апрель 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.
Язык: Английский
Процитировано
130
Asian Journal of Organic Chemistry, Год журнала: 2021, Номер 10(4), С. 711 - 748
Опубликована: Фев. 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
Язык: Английский
Процитировано
106
Chemical Science, Год журнала: 2023, Номер 14(21), С. 5545 - 5568
Опубликована: Янв. 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.
Язык: Английский
Процитировано
45
Chemical Communications, Год журнала: 2020, Номер 56(12), С. 1815 - 1818
Опубликована: Янв. 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.
Язык: Английский
Процитировано
80
ACS Catalysis, Год журнала: 2023, Номер 13(12), С. 7756 - 7794
Опубликована: Май 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.
Язык: Английский
Процитировано
40
Journal of the American Chemical Society, Год журнала: 2023, Номер 145(15), С. 8275 - 8284
Опубликована: Апрель 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.
Язык: Английский
Процитировано
29
ACS Catalysis, Год журнала: 2023, Номер 13(10), С. 6983 - 6993
Опубликована: Май 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.
Язык: Английский
Процитировано
25
Chemistry - A European Journal, Год журнала: 2024, Номер unknown
Опубликована: Фев. 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.
Язык: Английский
Процитировано
12