Nickel-catalyzed allylic defluorinative alkylation of trifluoromethyl alkenes with reductive decarboxylation of redox-active esters

Chemical Science, Journal Year: 2018, Volume and Issue: 10(3), P. 809 - 814

Published: Nov. 7, 2018

Synthesis of functionalized gem-difluoroalkenes was achieved through nickel-catalyzed allylic defluorinative alkylation trifluoromethyl alkenes with reductive decarboxylation redox-active esters.

Language: Английский

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Recent advances in the synthesis and applications of α-(trifluoromethyl)styrenes in organic synthesis

Chemical Communications, Journal Year: 2019, Volume and Issue: 55(90), P. 13486 - 13505

Published: Jan. 1, 2019

α-Trifluoromethylstyrene derivatives are versatile synthetic intermediates for the preparation of more complex fluorinated compounds. Much attention has been paid to these compounds by organic chemistry community, because they have successfully utilized in C-F bond activation a CF3 group, mainly including anionic SN2'-type substitution, cationic SN1'-type ipso-substitution and defluorinative functionalization with transition metals or photoredox catalysts. In addition, metal-catalyzed cycloaddition reactions α-trifluoromethylstyrenes developed construction cycloalkanes cycloalkenes containing fluoro trifluoromethyl groups. this review, we systematically summarized synthesis their applications chemistry, mechanisms were also discussed.

Language: Английский

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Site-Selective Defluorinative sp³ C–H Alkylation of Secondary Amides

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(17), P. 6395 - 6400

Published: April 27, 2021

A site-selective defluorinative sp3 C–H alkylation of secondary amides that rapidly and reliably incorporates gem-difluoroalkene motifs into previously unfunctionalized sites is disclosed. This protocol distinguished by its mild conditions, wide scope, exquisite site-selectivity, thus unlocking a new platform to introduce carbonyl isosteres at saturated hydrocarbon sites.

Language: Английский

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Recent advance in the C–F bond functionalization of trifluoromethyl-containing compounds

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(14), P. 3915 - 3942

Published: Jan. 1, 2021

The C–F bond is the strongest single in organic compounds.

Language: Английский

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Recent Advances in the Synthesis of Difluorinated Architectures from Trifluoromethyl Groups

Advanced Synthesis & Catalysis, Journal Year: 2021, Volume and Issue: 364(2), P. 234 - 267

Published: Nov. 29, 2021

Abstract Fluorine‐containing moieties are widely used in the pharmaceutical, agrochemical, and material fields. Thus, these structures of immense interest fields organic synthesis medicinal chemistry. Among various fluorinated groups, difluoromethyl unit has drawn increasing attention due to its unique pharmaceutical properties. In recent years, several methods for difluoromethylated compounds have been rapidly developed. However, most treat aromatic with excess difluoromethylating reagents, which often contain organometallic compounds, so transformations generally less environmentally friendly atom‐economical. this review, we summarize development new motifs or difluoroalkenes from trifluoromethylated trifluoromethyl alkenes via single C( sp 3 )−F bond cleavage. magnified image

Language: Английский

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Tetracoordinate Boron Intermediates Enable Unconventional Transformations

Accounts of Chemical Research, Journal Year: 2021, Volume and Issue: 54(9), P. 2298 - 2312

Published: April 14, 2021

ConspectusOrganoboron compounds are a class of multifunctional reagents for the construction carbon–carbon and carbon–heteroatom bonds in modern synthetic chemistry. The transformations organoboron usually carried out through tetracoordinate boron intermediates mainly include additions to unsaturated bonds, rearrangement reactions, transmetalation so on. Although great progress has been achieved improving intermediates, there still shortcomings, such as sparse activation modes, paucity reaction strategies difficulties stereoselective control. In this Account, we discuss our recent advances development unconventional based on design including following three topics: (1) C–B bonds; (2) C–C (3) application chiral boron.The new build is interest chemists. We have developed tandem reactions involving multiple selective borylations alkynes synthesis stable boron, domino-borylation-protodeboronation (DBP) strategy alkynes, highly regio-, stereo-, chemoselective Cu-catalyzed diborylation β-CF3-1,3-enynes cascade B–Cl/C–B cross-metathesis C–H bond borylation triarylboranes. also novel form because formation an enduring theme organic disclosed long distance or migration coupling partners 1,4-migrations nitrile oxide nitrilium migrations isocyanide intermediate, palladium-catalyzed Suzuki–Miyaura thioureas thioamides, copper-catalyzed atroposelective Michael-type addition, Catellani reaction. Moreover, terms control found that tricoordinate complex could activate water with Brønsted acidity, which successfully applied high enantioselectivity asymmetric catalytic reduction challenging indoles.This Account summarizes efforts using not only precise wide range diverse but acid indoles.

Language: Английский

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Chromium-Catalyzed Allylic Defluorinative Ketyl Olefin Coupling

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(30), P. 11602 - 11610

Published: July 22, 2021

Herein we report a chromium-catalyzed allylic defluorinative ketyl olefin coupling between aldehydes and α-trifluoromethyl alkenes, which provides novel efficient access to diverse gem-difluorohomoallylic alcohols. Remarkably, the high chemoselectivity of this reaction enables conversion formyl moiety in presence various easily reducible functionalities including ketone, organohalides, aziridine, sulfone, alkyne, unactivated alkene. The utility method is demonstrated by simple derivatizations attached hydroxyl group products. preliminary mechanistic investigations suggest pathway with rate-limiting C–C forming step followed facile β-fluoro elimination.

Language: Английский

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Synthetic Advantages of Defluorinative C−F Bond Functionalization

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(49)

Published: Aug. 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.

Language: Английский

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Synthesis of gem-Difluoroalkenes via Nickel-Catalyzed Allylic Defluorinative Reductive Cross-Coupling

ACS Catalysis, Journal Year: 2018, Volume and Issue: 8(10), P. 9245 - 9251

Published: Sept. 4, 2018

In this protocol, we report an allylic defluorinative reductive cross-coupling reaction for C–C bond formation. Under the Ni-catalysis challenging C(sp3)–F cleavage of trifluoromethyl-substituted alkenes was achieved with easily accessible primary, secondary and tertiary alkyl halides as coupling partners Zn-powder reducing agent. This process provides efficient convenient entry to gem-difluoroalkenes bearing various sensitive functional groups under mild conditions. Moreover, method proves be suitable late-stage functionalization multifunctional complex molecules.

Language: Английский

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NiH‐Catalyzed Migratory Defluorinative Olefin Cross‐Coupling: Trifluoromethyl‐Substituted Alkenes as Acceptor Olefins to Form gem‐Difluoroalkenes

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(13), P. 5398 - 5402

Published: Jan. 17, 2020

We report a NiH-catalyzed migratory defluorinative coupling between two electronically differentiated olefins. A broad range of unactivated donor olefins can be joined directly to acceptor containing an electron-deficient trifluoromethyl substituent in both intra- and intermolecular fashion form gem-difluoroalkenes. This shows site- chemoselectivity under mild conditions, with the formation tertiary or quaternary carbon center.

Language: Английский

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