Chemical Communications, Год журнала: 2024, Номер 60(35), С. 4656 - 4658
Опубликована: Янв. 1, 2024
A three-component carbonylation that provides a new method for the synthesis of ketones from Hantzsch esters has been developed.
Язык: Английский
Green Chemistry, Год журнала: 2023, Номер 25(20), С. 7971 - 7977
Опубликована: Янв. 1, 2023
Alkyl diacyl peroxides were demonstrated to be efficient alkylating reagents for the visible-light-induced 4CzIPN-catalyzed direct C–H alkylation of N -heteroaromatics.
Язык: Английский
Процитировано
51
Chem, Год журнала: 2024, Номер 10(3), С. 938 - 951
Опубликована: Янв. 10, 2024
Язык: Английский
Процитировано
27
ACS Catalysis, Год журнала: 2022, Номер 12(17), С. 10925 - 10937
Опубликована: Авг. 22, 2022
Atom transfer radical addition (ATRA) reaction of alkenes has had a significant impact on the field difunctionalization alkenes. Particularly, in three-component photo-ATRA-type processes, rich chemical space and structural diversity could be achieved by smart combination redox-active precursors third coupling components (e.g., halides, C-, N-, O-nucleophiles) under mild conditions. However, inherent complicated mechanisms involving chain or outer-sphere SET incipient intermediates have led to dearth general catalytic methods for highly enantioselective variants, especially those regarding asymmetric intermolecular C–O bond formation. Here, we report visible-light-induced copper-catalyzed with oxime esters carboxylic acids. In this process, cross-coupling between sp3-hybridized carbon radicals acids was enabled formation an aryl π-bond-engaged [σ + π]-copper complex. This working hypothesis renders naphthyl extended conjugation suitable substrates allows good stereocontrol. exhibits broad substrate scope high functional group tolerance respect each component, giving desired products generally yields enantioselectivity (>70 examples; up 97% ee). Preliminary experimental computational studies are also performed gain insight into mechanism stereoregulatory elements. finding provides promising platform development other benzylic-type radical-based reactions.
Язык: Английский
Процитировано
47
The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(8), С. 4925 - 4941
Опубликована: Янв. 27, 2023
Carbon monoxide is a cheap and abundant C1 building block that can be readily incorporated into organic molecules to rapidly build structural complexity. In this Perspective, we outline several recent (since 2015) examples of palladium-catalyzed carbonylations in streamlining complex natural product total synthesis highlight the strategic importance these carbonylation reactions corresponding synthesis. The selected include spinosyn A, callyspongiolide, perseanol, schizozygane alkaloids, cephanolides, bisdehydroneostemoninine related stemona alkaloids. We also provide our perspective about advancements future developments carbonylations.
Язык: Английский
Процитировано
39
Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(41)
Опубликована: Авг. 24, 2023
Radical single carbonylation reactions with CO constitute a direct and robust strategy toward various carbonyl compounds from readily available chemicals, have been extensively studied over the past decades. However, realizing highly selective catalytic systems for controlled radical double has remained substantial challenge, particularly more advanced multicomponent variants, despite their great potential value. Herein, we report visible-light-driven relay five-component aminocarbonylation reaction of unactivated alkenes using under metal-free conditions. This protocol provides access to valuable γ-trifluoromethyl α-ketoamides good yields high chemoselectivity. Crucial was identification distinct dual roles amine coupling partners, sequentially acting as electron donors formation photoactive donor-acceptor (EDA) complexes precursors then acceptor via nitrogen cations form carbamoyl radicals. Cross-coupling radicals acyl that are formed in an alkene-based process affords products.
Язык: Английский
Процитировано
25
Organic Letters, Год журнала: 2024, Номер 26(4), С. 933 - 938
Опубликована: Янв. 19, 2024
A visible-light-induced highly efficient C(sp3)–H amination of ethers with amides and azoles has been presented under mild conditions via a nitrogen- carbon-centered radical coupling process. This protocol successfully utilizes 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) tert-butyl nitrite (TBN) as cocatalysts to deliver the aminated products aerobic conditions. Notably, developed reaction features corresponding in good yields (up 93%) wide substrate scope. The mechanistic study indicates that C–N bond formation proceeds direct cross-coupling Preliminary biological activity analysis resulting have selective inhibitory on osteosarcoma (OS) cell lines are promising for use hits drug discovery.
Язык: Английский
Процитировано
14
Science, Год журнала: 2024, Номер 386(6723), С. 776 - 782
Опубликована: Ноя. 14, 2024
Unsymmetrical ureas are commonly found in pharmaceuticals and bioactive compounds. However, devising strategies to introduce two distinct amines selectively the construction of unsymmetrical remains a challenge. In this work, we use synchronous recognition strategy that takes advantage radical nucleophilic activation discriminate between secondary primary amines. Specifically, copper catalyst preferentially oxidizes species, whereas cobalt carbonylates produce amides. Coupling these fragments by cooperative catalysis produces with high selectivity, as showcased modification 41 biologically active compounds six drugs.
Язык: Английский
Процитировано
12
Chemical Communications, Год журнала: 2024, Номер 60(21), С. 2958 - 2961
Опубликована: Янв. 1, 2024
Visible-light-driven EDA complex-promoted ring-opening of cycloketone oxime esters to synthesise various 4-cyanoalkylated isoquinoline-1,3-diones with acryloylbenzamides was developed.
Язык: Английский
Процитировано
10
Journal of the American Chemical Society, Год журнала: 2025, Номер unknown
Опубликована: Фев. 17, 2025
1,2-Amino-difunctionalization reactions of alkenes allow the efficient introduction different functional groups and rapid construction valuable functionalized amines. In this respect, we report a copper-catalyzed 1,2-amino-alkoxycarbonylation unactivated with CO alkylamine precursors in presence Lewis acid additive. The novel protocol allows direct access to β-amino derivatives from easily available starting materials. presented methods feature high chemo- regioselectivities, good group tolerance, substrate scope including diverse bioactive compounds drug-like molecules. Mechanistic studies indicate that additive is key realizing umpolung addition nucleophilic aminyl radicals electron-rich alkenes, which represents an elegant activation strategy for radicals.
Язык: Английский
Процитировано
2
Chemical Science, Год журнала: 2022, Номер 13(45), С. 13466 - 13474
Опубликована: Янв. 1, 2022
Despite the ubiquity of alkylboronic acids in organic synthesis, their utility as alkyl radical precursors visible-light-induced photocatalytic reactions is limited by high oxidation potentials. In this study, we demonstrated that an inorganophosphorus compound can modulate potentials so they act precursors. We propose a mechanism based on results fluorescence quenching experiments, electrochemical 11B and 31P NMR spectroscopy, other techniques. addition, describe simple reliable alkylation method has good functional group tolerance be used for direct C-B chlorination, cyanation, vinylation, alkynylation, allylation, well late-stage functionalization derivatized drug molecules. Notably, selectively activated presence boronic pinacol ester.
Язык: Английский
Процитировано
30