Electrochemical Radical Formyloxylation–Bromination, −Chlorination, and −Trifluoromethylation of Alkenes

Organic Letters, Journal Year: 2019, Volume and Issue: 21(9), P. 3167 - 3171

Published: April 17, 2019

Given the versatility and value of structurally diverse organohalides CF3-containing compounds in organic synthesis, we reported a green, oxidant-free electrochemical method using undivided cells for radical bromination, chlorination trifluoromethylation–formyloxylation various alkenes with readily available halogen (NaCl, NaBr), trifluoromethyl (CF3SO2Na) sources, DMF as formyloxylation reagents. The protocol is operationally simple robust Cl–, Br– or CF3– was directly oxidized at anode, obviating need exogenous chemical oxidants.

Language: Английский

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Oxoammonium salts are catalysing efficient and selective halogenation of olefins, alkynes and aromatics

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: June 23, 2021

Abstract Electrophilic halogenation reactions have been a reliable approach to accessing organohalides. During the past decades, various catalytic systems developed for activation of haleniums. However, there is still short effective catalysts, which could cover and broad scope unsaturated compounds. Herein, TEMPO (2,2,6,6-tetramethylpiperidine nitroxide) its derivatives are disclosed as active catalysts electrophilic olefins, alkynes, aromatics. These stable, readily available, reactive enough activate haleniums including Br + , I even Cl reagents. This system applicable halogenations haloarylation olefins or dibromination were rarely realized in previous Lewis base catalysis acid catalysis. The high ability attributed synergistic model halogenating reagents, where carbonyl group halogen atom both activated by present

Language: Английский

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Expanding organofluorine chemical space: the design of chiral fluorinated isosteres enabled by I(i)/I(iii) catalysis

Chemical Science, Journal Year: 2021, Volume and Issue: 12(32), P. 10686 - 10695

Published: Jan. 1, 2021

Short aliphatic groups are prevalent in bioactive small molecules and play an essential role regulating physicochemistry molecular recognition phenomena.

Language: Английский

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Regioselective, catalytic 1,1-difluorination of enynes

Nature Chemistry, Journal Year: 2023, Volume and Issue: 15(11), P. 1515 - 1522

Published: Oct. 16, 2023

Fluorinated small molecules are prevalent across the functional small-molecule spectrum, but scarcity of naturally occurring sources creates an opportunity for creative endeavour in developing routes to access these important materials. Iodine(I)/iodine(III) catalysis has proven be particularly well-suited this task, enabling abundant alkene substrates readily intercepted by situ-generated λ3-iodanes and processed high-value (di)fluorinated products. These organocatalysis paradigms often emulate metal-based processes engaging π bond and, case styrenes, facilitating fluorinative phenonium-ion rearrangements generate difluoromethylene units. Here we demonstrate that enynes competent proxies thereby mitigating recurrent need aryl substituents, highly versatile homopropargylic difluorides generated operationally simple manner. The scope method is disclosed, together with application target synthesis (>30 examples, up >90% yield).

Language: Английский

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Aromatic halogenation using carborane catalyst

Chem, Journal Year: 2023, Volume and Issue: 10(1), P. 402 - 413

Published: Nov. 6, 2023

Language: Английский

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