Asymmetric Defluoroallylation of 4‐Trifluoromethylpyridines Enabled by Umpolung C−F Bond Activation**

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(21)

Published: March 11, 2022

Carbon-fluorine bond activation of the trifluoromethyl group represents an important approach to fluorine-containing molecules. While selective defluorinative functionalization reactions CF3 -containing substrates have been achieved by invoking difluorocarbocation, difluorocarboradical, or difluoroorganometallic species as key intermediates, transformations via fluorocarbanion mechanism only limited success. Furthermore, enantioselective transformation remained a formidable challenge. Here we report reaction 4-trifluoromethylpyridines involving difluoro(pyrid-4-yl)methyl anion intermediate, which was developed based upon our previous studies on N-boryl pyridyl chemistry. In particular, asymmetric defluoroallylation and -pyrimidines could be using Ir-catalysis forge difluoroalkyl-substituted chiral center.

Language: Английский

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Mechanochemical Defluorinative Acylation of ortho‐Hydroxyarylenaminones by CF₃‐Compounds: Synthesis of 3‐Acylchromones

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(12), P. 2026 - 2035

Published: May 22, 2023

Abstract An alternative strategy for the mechanochemical defluorinative acylation of ortho ‐hydroxyarylenaminones has been developed to synthesise 3‐acylchromones utilizing CF 3 ‐compounds via activation C−F bound trifluoromethyl group in presence ytterbia (Yb 2 O ). The current protocol tolerated a wide range coupling substrates access library diversely substituted under mechanochemically induced domino cyclisation mode. This is first report deflourinative transformation inert corresponding carbonyl functionality conditions.

Language: Английский

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Decarboxylation of β-boryl NHPI esters enables radical 1,2-boron shift for the assembly of versatile organoborons

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Sept. 14, 2023

In recent years, numerous 1,2-R shift (R = aliphatic or aryl) based on tetracoordinate boron species have been well investigated. the contrary, corresponding radical migrations, especially 1,2-boryl for construction of organoborons is still in its infancy. Given paucity and significance such strategies chemistry, it urgent to develop other efficient alternative synthetic protocols enrich these underdeveloped 1,2-boron before their fundamental potential applications could be fully explored at will. Herein, we demonstrated a visible-light-induced photoredox neutral decarboxylative cross-coupling reaction, which undergoes give translocated C-radical further capture versatile acceptors. The mild reaction conditions, good functional-group tolerance, broad β-boryl NHPI esters scope as acceptors make this protocol applicable modification bioactive molecules. It can expected that methodology will very useful tool an strategy primary via novel mode.

Language: Английский

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Modular assembly of versatile tetrasubstituted alkenyl monohalides from alkynyl tetracoordinate borons

Chem, Journal Year: 2023, Volume and Issue: 9(5), P. 1164 - 1181

Published: Feb. 6, 2023

Language: Английский

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Water-promoted defluorinative synthesis of fluoroalkylated 1,5-diazapentadienes by using (NH₄)₂CO₃ as an NH₂ and NH source

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(23), P. 9672 - 9679

Published: Jan. 1, 2023

A H 2 O-promoted and (NH 4 ) CO 3 -enabled defluoroiminization reaction of fluoroalkyl alkenes for the synthesis fluoroalkylated 1,5-diazapentadienes has been developed.

Language: Английский

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