Organic Letters, Год журнала: 2022, Номер 24(22), С. 4075 - 4080
Опубликована: Июнь 1, 2022
We describe a catalytic strategy for direct single C(sp3)-F bond alkylation of trifluoromethylbenzimidazoles under photoinduced thiol catalysis process. The CO2 radical anion (CO2•-) proved to be the most efficient single-electron reductant realize such transformation. spin-center shift generated intermediate is key step in realizing C-F activation mild conditions with high efficiency.
Язык: Английский
Nature Communications, Год журнала: 2022, Номер 13(1)
Опубликована: Янв. 17, 2022
Under visible light irradiation, o-phosphinophenolate functions as an easily accessible photoredox catalyst to activate trifluoromethyl groups in trifluoroacetamides, trifluoroacetates, and (hetero)arenes deliver corresponding difluoromethyl radicals. It works relay with a thiol hydrogen atom transfer (HAT) enable selective defluoroalkylation hydrodefluorination. The reaction allows for the facile synthesis of broad scope difluoromethylene-incorporated carbonyl (hetero)aromatic compounds, which are valuable fluorinated intermediates interest pharmaceutical industry. ortho-diphenylphosphino substituent, is believed facilitate photoinduced electron transfer, plays essential role redox reactivity phenolate. In addition groups, pentafluoroethyl could also be selectively defluoroalkylated.
Язык: Английский
Процитировано
106
Nature Chemistry, Год журнала: 2023, Номер 15(12), С. 1683 - 1692
Опубликована: Ноя. 13, 2023
Язык: Английский
Процитировано
78
Accounts of Chemical Research, Год журнала: 2022, Номер 56(2), С. 169 - 186
Опубликована: Дек. 26, 2022
ConspectusThe past decades have witnessed tremendous progress on radical reactions. However, in comparison with carbon, nitrogen, oxygen, and other main group element centered radicals, the synthetic chemistry of boron radicals was less studied, mainly due to high electron-deficiency instability such 3-center-5-electron species. In 1980s, Roberts co-workers found that coordination a Lewis base (amines or phosphines) center could form 4-center-7-electron boryl (Lewis base-boryl LBRs) are be more stable. only limited applications were developed. 2008, Curran achieved breakthrough discovery N-heterocyclic carbene (NHC) which enable range reduction polymerization Despite these exciting findings, powerful valuable LBRs would expected, given structures reactivities easily modulated, provide ample opportunities discover new this Account, summary our key contributions LBR-enabled borylation reactions selective activation inert carbon-heteroatom bonds will presented.Organoboron compounds shown versatile chemical society, their syntheses rely principally ionic The development mechanistically different allows synthesizing products inaccessible by traditional methods. For purpose, we progressively developed series NHC-boryl mediated chemo-, regio-, stereoselective alkenes alkynes, wide variety structurally diverse organoboron molecules successfully prepared. utility borylated also demonstrated. Furthermore, disclosed photoredox protocol for oxidative generation enabled useful defluoroborylation arylboration reactions.Selective bond is an ideal way convert simple starting materials value-added products, while cleavage bonds, particular chemoselectivity control when multiple identical present similar environments, remains long-standing challenge. We envisaged finely tuning properties might solution address Recently, 4-dimethylaminopyridine (DMAP)-boryl promoted sequential C-F functionalization trifluoroacetic acid derivatives, α-C-F selectively snipped via spin-center shift mechanism. This strategy enables facile conversion abundantly available highly mono- difluorinated molecules. Encouraged finding, further three-step sequence construct all-carbon quaternary centers from trichloromethyl groups, where three C-Cl cleaved rational choice suitable precursors each step. dehydroxylative alkylation α-hydroxy carboxylic derivatives achieved, allowing efficient some biomass platform value products.
Язык: Английский
Процитировано
73
Organic Letters, Год журнала: 2023, Номер 25(32), С. 6062 - 6066
Опубликована: Авг. 8, 2023
The elaboration of step-economy and catalytic approaches for accessing diverse fluorinated heterocyclics is highly desirable. Described herein a radical-polar crossover enabled three-component cyclization to polysubstituted fluoropyrazoles by using CF2Br2 as novel C1F1 synthon. Mechanistic experiments revealed that the in situ generation reactive intermediate gem-difluorovinylimine ion key this transformation. This protocol unlocks reactivity adds significant synthetic values fluorine chemistry.
Язык: Английский
Процитировано
67
Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(49)
Опубликована: Авг. 22, 2023
Abstract Much progress has been made in the development of methods to both create compounds that contain C−F bonds and functionalize bonds. As such, are becoming common versatile synthetic functional handles. This review summarizes advantages defluorinative functionalization reactions for small molecule synthesis. The coverage is organized by type carbon framework fluorine attached mono‐ polyfluorinated motifs. main challenges, opportunities advances discussed each class organofluorine. Most text focuses on case studies illustrate how defluorofunctionalization can improve routes targets or properties enable unique mechanisms reactions. broader goal showcase incorporating exploiting design routes, improvement specific advent new methods.
Язык: Английский
Процитировано
60
Nature Chemistry, Год журнала: 2024, Номер 16(6), С. 988 - 997
Опубликована: Март 5, 2024
Язык: Английский
Процитировано
46
Nature Communications, Год журнала: 2024, Номер 15(1)
Опубликована: Янв. 10, 2024
Abstract Bioisosteric design has become an essential approach in the development of drug molecules. Recent advancements synthetic methodologies have enabled rapid adoption this strategy into discovery programs. Consequently, conceptionally innovative practices would be appreciated by medicinal chemistry community. Here we report expeditous method for synthesizing aryl difluoromethyl bicyclopentane (ADB) as a bioisostere benzophenone core. This involves merger light-driven C−F bond activation and strain-release under catalysis newly designed N -anionic-based organic photocatalyst. defluorinative coupling methodology enables direct conversion wide variety commercially available trifluoromethylaromatic bonds (more than 70 examples) corresponding bicyclo[1.1.1]pentanes (BCP) arenes/difluoromethyl BCP boronates single step. The can also applied to [3.1.1]and [4.1.1]propellane systems, providing access analogues with different geometries. Moreover, successfully used protocol rapidly prepare ADB-substituted bioactive molecule Adiporon. Biological testing shown that ADB scaffold potential enhance pharmacological properties benzophenone-type candidates.
Язык: Английский
Процитировано
32
Case Studies in Chemical and Environmental Engineering, Год журнала: 2024, Номер 9, С. 100623 - 100623
Опубликована: Янв. 14, 2024
Alarming concern over the persistence and toxicity of per- polyfluoroalkyl substances (PFAS) in environment has created an imperative need for designing redesigning strategies their detection remediation. Conventional PFAS removal technologies that uses physical, chemical, or biological methods. Increase diversity quantity entering necessitated developing more advanced integrated removal. Despite advances reported this domain, there exist a huge research gap to be mentored tackle problems associated with mitigation combined wide variety environment. The possibility combine other emerging contaminants poses additional threat existing treatment methods thereby stressing continuous monitoring updating processes. This review work aims at understanding structure, entry, fate different types Further in-depth discussion regarding levels is elaborated review. process description recent remediation techniques along significance, limitations integration discussed detail. detailed outlook on advantages insight into recently developed outlined
Язык: Английский
Процитировано
26
Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(16), С. 1913 - 1928
Опубликована: Апрель 24, 2024
Comprehensive Summary Organic fluorine compounds are ubiquitous and pivotally important organic molecules, yet their activation transformation have long been a formidable challenge due to the high energy low reactivity of C—F bonds. electrosynthesis, an environmentally benign synthetic method in chemistry, enables myriad chemical transformations without need for external redox reagents. In recent years, electrochemistry has emerged as powerful tool achieving bonds fluorine‐containing compounds. This review aims succinctly recapitulate latest advancements electrochemical defluorinative delve into reaction design, mechanistic insights, developmental prospects these methods. Key Scientists 1959, Lund was first pioneer electroreduction CF 3 CH group. Electrochemistry lately provided new opportunities efficient conversion fluorides. 2020, Zhou coworkers discovered carboxylation α‐CF alkenes. Lambert colleagues reported electrophotocatalytic amination aryl Electrochemical hydrodefluorination trifluoromethylketones developed by Lennox 2021. same year, Wang Guo disclosed radical alkylation alkenes with Katritzky salts alkyl precursors. Subsequently, Wu Liao described transition‐metal‐free, site‐selective arylation polyfluoroarenes (het)arenes using paired electrophotocatalysis. 2023, numerous efforts were made achieve bond activation. Xia organoboron‐controlled chemoselective sequential (deutero)hydrodefluorination trifluoroacetamides.
Язык: Английский
Процитировано
26
Chemical Science, Год журнала: 2024, Номер 15(8), С. 2712 - 2724
Опубликована: Янв. 1, 2024
Frustrated Lewis pair (FLP) bond activation chemistry has greatly developed over the last two decades since seminal report of metal-free reversible hydrogen activation. Recently, FLP systems have been utilized to allow monoselective C-F (at equivalent sites) in polyfluoroalkanes. The problem 'over-defluorination' functionalization polyfluoroalkanes (where multiple fluoro-positions are uncontrollably functionalized) a long-standing chemical fluorocarbon for 80 years. mediated is complementary other solutions address and offers several advantages unique opportunities. This perspective highlights some these opportunities places development into context wider effort overcome 'over-defluorination'.
Язык: Английский
Процитировано
20