Synthesis of Fluorinated Compounds by Nickel-Catalyzed Defluorinative Cross-Coupling Reactions

ACS Catalysis, Год журнала: 2023, Номер 13(18), С. 12238 - 12268

Опубликована: Сен. 1, 2023

Organofluorine compounds have attracted extensive attention in various industrial fields due to their unique chemical and physical properties. Despite increasing demand a wide range of scientific fields, the synthesis organofluorine still faces several problems, such as difficulties handling fluorinating reagents control chemoselectivity. Compared with formation C–F bonds, activation functionalization carbon–fluorine bonds is very important but challenging topic synthetic chemistry. Due properties nickel, Ni-catalyzed defluorinative cross-couplings been greatly developed past few decades powerful strategies for construction fluorinated organic compounds. This Review summarizes advances cross-coupling aryl fluorides, gem-difluorovinyl trifluoromethyl

Язык: Английский

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Metal-free, visible-light driven α-C(sp³)–H gem-difluoroallylation of glycine derivatives with trifluoromethyl alkenes and 1,3-enynes

Green Chemistry, Год журнала: 2023, Номер 25(17), С. 6733 - 6738

Опубликована: Янв. 1, 2023

A metal free, visible-light driven α-C(sp 3 )−H gem-difluoroallylation of glycine derivatives with CF -alkenes and 1,3-enynes is presented under redox-neutral conditions good yields excellent functional group compatibility.

Язык: Английский

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Palladium‐Catalyzed Cascade Heck Coupling and Allylboration of Iododiboron Compounds via Diboryl Radicals

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(18)

Опубликована: Март 6, 2024

Geminal bis(boronates) are versatile synthetic building blocks in organic chemistry. The fact that they predominantly serve as nucleophiles the previous reports, however, has restrained their potential. Herein we disclose ambiphilic reactivity of α-halogenated geminal bis(boronates), which first catalytic utilization was accomplished by merging a formal Heck cross-coupling with highly diastereoselective allylboration aldehydes or imines, providing new avenue for rapid assembly polyfunctionalized boron-containing compounds. We demonstrated this cascade reaction is efficient and compatible various functional groups, wide range heterocycles. In contrast to classical Pd(0/II) scenario, mechanistic experiments DFT calculations have provided strong evidence cycle involving Pd(I)/diboryl carbon radical intermediates.

Язык: Английский

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Deoxygenative Haloboration and Enantioselective Chloroboration of Carbonyls

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(50), С. 22870 - 22876

Опубликована: Дек. 7, 2022

Deoxygenative difunctionalization of carbonyls affords a straightforward and effective route to construct geminal dual functionalized motifs. However, the research in this field is very challenging due strong bond dissociation energies C–O double or subsequently formed bond. Herein, we report highly efficient deoxygenative haloboration aldehydes generate secondary α-haloboronates. Meanwhile, difficult-to-obtain tertiary α-haloboronates can be also readily prepared via same strategy with ketones. Furthermore, enantioselective chloroboration was successfully achieved give chiral α-chloroboronates, important intermediates access enantioenrich multisubstituted stereocenters. These versatile products surprisingly attained through simple mild process remarkable substrate scope expansion functional group tolerance. Additionally, these reactions proceed well on large scales, giving more practical values application.

Язык: Английский

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Electrochemical Synthesis of gem‐Difluoro‐ and γ‐Fluoro‐Allyl Boronates and Silanes

Chemistry - A European Journal, Год журнала: 2022, Номер 28(66)

Опубликована: Сен. 6, 2022

Abstract The electrochemical synthesis of fluorinated allyl silanes and boronates was disclosed. addition electrogenerated boryl or silyl radicals onto many α‐trifluoromethyl α‐difluoromethylstyrenes in an undivided cell allowed the formation a large panel synthetically useful gem ‐difluoro γ‐fluoroallyl (64 examples, from 31 % to 95 yield). In addition, scale up reactions under continuous flow showcased using reactor with promising volumetric productivity (688 g.L −1 .h 496 ). Moreover, synthetic utility these building blocks highlighted through versatile transformations. Finally, plausible reaction mechanisms were suggested explain products.

Язык: Английский

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Visible-light-promoted defluorinated alkylation of trifluoromethyl alkenes initiated by radical [1,2]-Brook rearrangement: facile synthesis ofgem-difluoro homoallylic alcohol derivatives

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(8), С. 1981 - 1987

Опубликована: Янв. 1, 2023

A photoinduced radical [1,2]-Brook rearrangement/defluorinated alkylation reaction of α-trifluoromethyl alkenes with α-silyl alcohols was developed for facile access to gem -difluoro homoallylic alcohol derivatives.

Язык: Английский

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Mechanochemical Synthesis of α‐halo Alkylboronic Esters

Advanced Science, Год журнала: 2024, Номер 11(33)

Опубликована: Июль 3, 2024

α-halo alkylboronic esters, acting as ambiphilic synthons, play a pivotal role versatile intermediates in fields like pharmaceutical science and organic chemistry. The sequential transformation of carbon-boron carbon-halogen bonds into broad range carbon-X allows for programmable bond formation, facilitating the incorporation multiple substituents at single position streamlining synthesis complex molecules. Nevertheless, synthetic potential these compounds is constrained by limited reaction patterns. Additionally, conventional methods often necessitate use bulk toxic solvents, exhibit sensitivity to air/moisture, rely on expensive metal catalysts, involve extended times. In this report, ball milling technique introduced that overcomes limitations, enabling external catalyst-free multicomponent coupling aryl diazonium salts, alkenes, simple halides. This approach offers general straightforward method obtaining diverse array thereby paving way extensive utilization synthons fine chemicals.

Язык: Английский

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Nickel‐Catalyzed Unsymmetrical Bis‐Allylation of Alkynes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(17)

Опубликована: Фев. 24, 2023

The catalytic bis-allylation of alkynes is an important but challenging protocol to construct all-carbon tetra-substituted alkenes. Particularly, the unsymmetrical remains as underexplored task date. We herein report unprecedented by simultaneously utilizing electrophilic trifluoromethyl alkene and nucleophilic allylboronate allylic reagents. With aid robust Ni0 /NHC catalysis, valuable skipped trienes can be obtained in high regio- stereo-selectivities under mild conditions. Mechanistic studies indicate that reaction may proceed through a β-fluorine elimination nickelacycle followed transmetalation step with allylboronate. present method exhibits good tolerance various functional groups. Besides, triene products undergo array elaborate transformations, which highlights potential applications this strategy.

Язык: Английский

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Nickel-Catalyzed Enantioselective Dearomative Heck-Reductive Allylic Defluorination Reaction of Indoles

Organic Letters, Год журнала: 2023, Номер 25(33), С. 6122 - 6127

Опубликована: Авг. 14, 2023

Herein, we describe a nickel-catalyzed asymmetric dearomative aryl-difluoroallylation reaction of indoles with α-trifluoromethyl alkenes as an electrophilic coupling partner. The proceeds via cascade sequence involving Heck cyclization and reductive allylic defluorination. A series gem-difluoroallyl substituted indolines are obtained in moderate to good yields (36-77% yield) excellent enantioselectivity (up 99% ee). features broad functional group tolerance, scaled-up synthesis, late-stage diversification.

Язык: Английский

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Direct Synthesis of β-Amino Boronates via Amide α-C–H Bond Activation and C(sp³)–C(sp³) Coupling under Dual Ni/Photoredox Catalysis

ACS Catalysis, Год журнала: 2023, Номер 14(1), С. 547 - 553

Опубликована: Дек. 26, 2023

Direct transformations of readily available amines or amides via C–H bond functionalization could provide a fast route for accessing complex molecules. While various groups have been successfully incorporated into the α position nitrogen atom with photoredox system activation, couplings functionalized alkyl halides are still very challenging. Herein, we report direct and convenient protocol β-amino boronates through C(sp3)–C(sp3) coupling α-bromoboronates. The mild conditions allow good functional group tolerance broad scope. application method in late-stage modification molecules further demonstrates its great potential organic synthesis. Mechanistic studies were also conducted, catalytic cycle is proposed.

Язык: Английский

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