Visible-Light-Induced Difluoroalkylation of Alkenes and Alkynes with Fluoro-Containing Hypervalent Iodane (III) Reagents Under Photo-Catalyst-Free Conditions

Liu, Ruiyue; Zhou, Ningning; Zhao, Tingting; Zhang, Ying; Wang, Kun; Zhao, Xia; Lu, Kui

doi:10.1021/acs.joc.2c02488

Cited by 7 publications

(3 citation statements)

References 45 publications

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“…Liu, Zhou, and Lu developed a hydrodifluoroalkylation reagent which enabled them to functionalize different unactivated alkenes and also alkynes (Scheme 4C). 39 Recently, the same group also developed an elegant multicomponent reaction system (Scheme 4D) in which fluoroalkyl radicals first add to the double bond of a styrene derivative, and the newly formed benzylic radical then adds to an electron-poor nitrogen heterocycle. 40 The developed multicomponent system requires two additional equivalents of a HIR-based oxidant PIFA.…”

Section: Radical Addition To Alkenes and Alkynesmentioning

confidence: 99%

Transformations based on direct excitation of hypervalent iodine(iii) reagents

Narobe

Koenig

2023

Org. Chem. Front.

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Section: Radical Addition To Alkenes and Alkynesmentioning

confidence: 99%

Transformations based on direct excitation of hypervalent iodine(iii) reagents

Narobe

Koenig

2023

Org. Chem. Front.

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“…[98] Although the method needs a quantitative amount of the expensive Hanzsch ester, it should be notified that the Zselective addition was accomplished. [98] Very recently, Lu reported a photocatalyst-free visible light-induced direct 2,2difluoroacetylation using the hypervalent iodane (III) reagent (Figure 22, (C)) [99] Installation of the gem-difluoromethylene group into organic molecules still remains a big challenge in synthetic organic chemistry.…”

Section: P E R S O N a L A C C O U N T T H E C H E M I C A L R E C O R Dmentioning

confidence: 99%

Synthesis of Selectively gem‐Difluorinated Molecules; Chiral gem‐Difluorocyclopropanes via Chemo‐Enzymatic Reaction and gem‐Difluorinated Compounds via Radical Reaction

Itoh

Hayase

Nokami

2023

The Chemical Record

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The incorporation of fluorine atoms into an organic compound can alter the chemical reactivity or biological activity of the resulting compound due to the strong electron withdrawing nature of the fluorine atom. We have synthesized many original gem‐difluorinated compounds and described the results in four sections. The first section describes the synthesis of optically active‐gem‐difluorocyclopropanes via the chemo‐enzymatic reaction; we applied these compounds to liquid crystalline molecules, then further discovered a potent DNA cleavage activity for the gem‐difluorocyclopropane derivatives. The second section describes the synthesis of selectively gem‐difluorinated compounds via a radical reaction; we synthesized fluorinated analogues of a sex pheromone of the male African sugarcane borer, Eldana saccharina, and used the compounds as proof for investigating the origin of pheromone molecule recognition on the receptor protein. The third involves the synthesis of 2,2‐difluorinated‐esters by visible light‐driven radical addition of 2,2‐difluoroacetate with alkenes or alkynes in the presence of an organic pigment. The last section describes the synthesis of gem‐difluorinated compounds via the ring‐opening of gem‐difluorocyclopropanes. We further developed a novel method of synthesizing gem‐difluorohomoallylic alcohols via the ring‐opening of gem‐difluorocyclopropane and aerobic oxidation by photo‐irradiation in the presence of an organic pigment. Since gem‐difluorinated compounds that were prepared by the present method have two olefinic moieties with a different reactivity at the terminal position, we accomplished the synthesis of four types of gem‐difluorinated cyclic alkenols via the ring‐closing‐metathesis (RCM) reaction.

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“…With these fluorinated iodane(III) reagents in hand, we developed a photoinduced three-component difluoroalkylation of quinoxalinones with alkenes, a visiblelight-triggered radical cyclization of alkynoates to 3-fluoroalkylated coumarins, and a visible-light-induced hydrodifluoroalkylation of alkenes and alkynes. [14][15][16] Herein, we report a visible-light-induced C(3) difluoroalkylation of quinoxalin-2(1H)-ones 1 with these difluoroiodane(III) reagents under catalyst-free conditions (Scheme 1, equation 7).…”

Section: Letter Synlett Dane(iii)mentioning

confidence: 99%

Visible-Light-Induced C-3 Difluoroalkylation of Quinoxalin-2(1H)-ones with Difluoroiodane(III) Reagents under Catalyst-Free Conditions

Qin

Zhou

Wang

et al. 2023

Synlett

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A visible-light-induced radical difluoroalkylation of quinoxalin-2(1H)-ones by hypervalent iodine based difluoroalkylation reagents was developed. To facilitate the final oxidative step, [Bis(trifluoroacetoxy)iodo]benzene (PIFA) was employed as oxidant. Moreover, a one-pot protocol of this transformation was realized by generating the difluoroalkylation reagent in situ. The readily accessible reagents and the mild reaction conditions make this reaction an alternative and practical strategy for the synthesis of C3-difluoroalkylated quinoxalin-2(1H)-ones.

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Visible-Light-Induced Difluoroalkylation of Alkenes and Alkynes with Fluoro-Containing Hypervalent Iodane (III) Reagents Under Photo-Catalyst-Free Conditions

Cited by 7 publications

References 45 publications

Transformations based on direct excitation of hypervalent iodine(iii) reagents

Transformations based on direct excitation of hypervalent iodine(iii) reagents

Synthesis of Selectively gem‐Difluorinated Molecules; Chiral gem‐Difluorocyclopropanes via Chemo‐Enzymatic Reaction and gem‐Difluorinated Compounds via Radical Reaction

Visible-Light-Induced C-3 Difluoroalkylation of Quinoxalin-2(1H)-ones with Difluoroiodane(III) Reagents under Catalyst-Free Conditions

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