Chemical Science, Год журнала: 2024, Номер 15(34), С. 13800 - 13806
Опубликована: Янв. 1, 2024
Metathesis reactions have been established as a powerful tool in organic synthesis. While great advances were achieved double-bond metathesis, like olefin metathesis and carbonyl single-bond has received less attention the past decade. Herein, we describe first C(sp
Язык: Английский
Chemical Reviews, Год журнала: 2024, Номер 124(8), С. 4822 - 4862
Опубликована: Апрель 2, 2024
The synthesis of organic compounds efficiently via fewer steps but in higher yields is desirable as this reduces energy and reagent use, waste production, thus environmental impact well cost. reactivity C–H bonds ortho to fluorine substituents (poly)fluoroarenes with metal centers enhanced relative meta para positions. Thus, direct functionalization without prefunctionalization becoming a significant area research chemistry. Novel selective methodologies functionalize (poly)fluorinated arenes by taking advantage the C–F are continuously being developed. This review summarizes reasons for consequent developments valuable (poly)fluoroarene-containing compounds.
Язык: Английский
Процитировано
16
ACS Catalysis, Год журнала: 2021, Номер 11(19), С. 11960 - 11965
Опубликована: Сен. 13, 2021
A cross-electrophile coupling between gem-difluorinated cyclopropanes and 2,2-difluorovinyl tosylate via dual Ni/Pd cooperative catalysis under mild reaction conditions is presented. Various structurally unique organofluorine compounds bearing both monofluoroalkene gem-difluoroalkene moieties can be effectively afforded in good yields with a high (Z)-selectivity. The synthetic utility of this protocol has been successfully demonstrated by the late-stage modification series complex bioactive molecules.
Язык: Английский
Процитировано
60
Organic Letters, Год журнала: 2022, Номер 24(11), С. 2093 - 2098
Опубликована: Март 11, 2022
Palladium-catalyzed synthesis of 3-acyl and -allyl indoles has been realized by merging nucleophilic cyclization ortho-alkynylanilines with ring opening three-membered rings such as cyclopropenones gem-difluorinated cyclopropanes. These functionalized were obtained in moderate to high yields stereoselectivity both cases. This protocol provides an alternative method toward under mild redox-neutral conditions.
Язык: Английский
Процитировано
53
ACS Catalysis, Год журнала: 2022, Номер 12(11), С. 6495 - 6505
Опубликована: Май 17, 2022
Controlling the selectivity of synthetically useful reactions has been a longstanding objective organic chemistry. We report regiodivergent synthetic protocol allowing access to diverse fluorinated 1,5-dienes through Pd/NHC-catalyzed ring-opening allylation gem-difluorocyclopropanes. Density functional theory (DFT) calculations on regioselectivity-determining transition states provided critical insight into design NHC ligand for switching regioselectivity. Consistent with DFT predictions, N-heterocyclic carbene (NHC) ligands bulky ortho substituents favored branched allylation, IHept providing > 20:1 branched/linear less hindered such as IMes thermodynamically more stable linear products. were able carry out late-stage modification various complex molecules using this protocol. Our ligand-controlled approach provides efficient regioisomeric from same starting materials and constitutes valuable addition toolbox diversity-oriented synthesis.
Язык: Английский
Процитировано
50
ACS Catalysis, Год журнала: 2022, Номер 12(15), С. 8857 - 8867
Опубликована: Июль 10, 2022
The unique properties of the fluorine-containing compounds and their widespread applications raise demand for dependable synthetic methods on precise introduction substituents into organic molecules. Herein, a site-divergent fluoroallylation olefins that can incorporate fluoroallyl motif different alkenyl C–H sites is disclosed. gem-Difluorinated cyclopropanes are employed as sources via rhodium-catalyzed C–C bond activation. This strategy provide two regioisomeric fluorinated skipped dienes in good yields with excellent site-selectivity. resulting products serve useful building blocks to access various molecules isosteric β, γ-unsaturated amides, which promising be exploited medicinal chemistry. Mechanistic studies revealed electronic property rhodium catalysts crucial controllable site-selectivity, providing more insights beyond methodology tuning selectivity metal catalysts.
Язык: Английский
Процитировано
48
ChemCatChem, Год журнала: 2022, Номер 14(24)
Опубликована: Авг. 11, 2022
Abstract gem ‐Difluorocyclopropanes (F 2 CPs) have aroused considerable attention not only from the structural perspective but also due to their ability participate in various valuable transformations. This Review summarizes advances catalytic ring‐opening reactions of ‐F CPs, especially emphasizing reactivities and applications those non‐activated ones under transition‐metal catalysis. Their achievements, synthetic limitations are discussed with aim stimulate enthusiasm for further development.
Язык: Английский
Процитировано
47
Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(23)
Опубликована: Апрель 4, 2023
Defluorinative manipulation of polyfluorinated molecules has shown great promise due to its granting synthetic versatility inert C-F bonds. The development chemo-, stereo- and regioselective strategies realize highly efficient formation either the linear/branched or E/Z products from gem-difluorocyclopropanes (gem-F2 CPs) is a challenging task. Herein, we have realized palladium/NHC-catalyzed fluoroallylation/annulation hydrazones with gem-F2 CPs that incorporate hydrazone N2 moiety into products. thermodynamically unstable fluorinated E-allylation aryl ketone were obtained for first time, while di-alkyl yielded monofluorinated branched selectivity under similar reaction conditions. With aldehyde hydrazones, two kinds pyrazoles via defluorinative allylation/annulation cascade, in which different carbon atoms could be incorporated pyrazole rings regiospecifically. DFT calculations revealed divergent was kinetically controlled final C-C bond proceeded through 7-membered TS.
Язык: Английский
Процитировано
36
Journal of the American Chemical Society, Год журнала: 2023, Номер 146(1), С. 24 - 32
Опубликована: Окт. 13, 2023
Developing new strategies to enable chemo- and regioselective reductions is an important topic in chemical research. Herein, efficient Pd/IPr
Язык: Английский
Процитировано
33
Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(42)
Опубликована: Авг. 12, 2023
Abstract An unprecedented Pd‐catalyzed fluorinative bifunctionalization of aziridines and azetidines was successfully developed via regioselective C−C C−F bond cleavage gem‐difluorocyclopropanes, leading to various β,β′‐bisfluorinated amines β,γ‐bisfluorinated amines. This reaction achieved by incorporating a 2‐fluorinated allyl group fluorine atom scissored from gem‐difluorocyclopropane in 100 % economy for the first time. The mechanistic investigations indicated that underwent amine attacking palladium complex generate η 2 ‐coordinated N‐allyl aziridine followed fluoride ligand transfer affording final β‐ γ‐fluorinated
Язык: Английский
Процитировано
30
Green Chemistry, Год журнала: 2023, Номер 25(8), С. 3095 - 3102
Опубликована: Янв. 1, 2023
A regiodivergent electrochemical defluorocarboxylation of gem -difluorocyclopropanes is realized, providing access to branched and linear carboxylated monofluorinated alkenes.
Язык: Английский
Процитировано
27