Synthesis of monofluoroalkenes through selective hydrodefluorination of gem-difluoroalkenes with Red-Al®

Xiao, Juan; Dai, Wenpeng; Cao, Song

doi:10.1039/c5ra04221f

Cited by 36 publications

(16 citation statements)

References 49 publications

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“…4a). Notably, during reaction optimization the fluorinated 1,3-enyne [61][62][63][64][65][66][67][68] 9a was observed. In addition, treatment of the 1,3enyne 1a with a reduced amount of NFSI afforded compound 9a along with targeted 4a.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of difluoromethylated allenes through trifunctionalization of 1,3-enynes

Muhammad

Jiao

et al. 2020

Nat Commun

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Organofluorine compounds have shown their great value in many aspects. Moreover, allenes are also a class of important compounds. Fluorinated or fluoroalkylated allenes might provide an option as candidates for drug and material developments, as allenes allow a great number of valuable transformations. Herein, we report a metal-free synthesis of difluoromethylated allenes via regioselective trifunctionalization of 1,3-enynes. This method proceeds through double C-F bond formation with concomitant introduction of an amino group to the allene. Synthetic applications are conducted and preliminary mechanistic studies suggest that a twostep pathway is involved. DFT calculations revealed an unusual dibenzenesulfonimideassisted fluorination/fluoroamination with NFSI. In addition, kinetic reaction study revealed the induction period of both major and side products to support the proposed reaction mechanism. This work offers a convenient approach for the synthesis of a range of difluoromethylated allenes and is also a rare example of trifunctionalization of 1,3-enynes.

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Section: Resultsmentioning

confidence: 99%

Synthesis of difluoromethylated allenes through trifunctionalization of 1,3-enynes

Muhammad

Jiao

et al. 2020

Nat Commun

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“…As shown by Wu, Cao, and co-workers, Red-Al [sodium bis(2-methoxyethoxy)aluminum hydride] allowed the hydrodefluorination of gem-difluoroalkenes with good E selectivity (Scheme 25). 38 However, the reaction was only carried out with styrene derivatives as substrates.…”

Section: Syn Thesismentioning

confidence: 99%

“…The selective hydrodefluorination of 1,1-diaryl-2,2-difluoroethenes in the presence of Red-Al gave the corresponding 1,2-diaryl-1-fluoroethenes in high yields (Scheme 106). 38 In 2017, Ito and co-workers reported the copper(I)-catalyzed stereoselective hydrodefluorination of β,β-difluorostyrenes. 39 While the method was most efficient for the…”

Section: Scheme 105 Copper-catalyzed Borylation Of Gem-difluoroalkenesmentioning

confidence: 99%

Synthesis of Monofluoroalkenes: A Leap Forward

2018

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Monofluoroalkenes have found wide application in organic chemistry, medicinal chemistry, and materials science. This review summarizes the most recent advances made regarding the preparation of monofluoroalkenes, covering the period between October 2010 and September 2017. This review is divided in three main parts, one for each possible substitution pattern, namely di-, tri-, and tetrasubstituted. Then, for each class, further subclassification is made according to the reaction type.1 Introduction2 Disubstituted Monofluoroalkenes2.1 Disubstituted α-Monofluoroalkenes2.2 Disubstituted β-Monofluoroalkenes3 Trisubstituted Monofluoroalkenes4 Tetrasubstituted Monofluoroalkenes5 Conclusions

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“…Substrates 1a−f,h−k,m were synthesized according to previously reported procedures. 15 Substrates 1g,l were synthesized according to methods in the literature. 16 Substrate Z-1a was prepared according to reported methods.…”

Section: ■ Conclusionmentioning

confidence: 99%

Copper- and Nickel-Catalyzed Cross-Coupling Reaction of Monofluoroalkenes with Tertiary, Secondary, and Primary Alkyl and Aryl Grignard Reagents

et al. 2018

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A highly efficient cross-coupling reaction of monofluoroalkenes with tertiary, secondary, and primary alkyl and aryl Grignard reagents in the presence of a catalytic amount of copper or nickel catalyst, respectively, has been developed. The reactions proceeded smoothly at room temperature, providing (E)-alkene isomers in moderate to high yields. Plausible mechanisms of the Ni-catalyzed coupling reaction of monofluoroalkene with Grignard reagents are suggested.

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Synthesis of monofluoroalkenes through selective hydrodefluorination of gem-difluoroalkenes with Red-Al®

Cited by 36 publications

References 49 publications

Synthesis of difluoromethylated allenes through trifunctionalization of 1,3-enynes

Synthesis of difluoromethylated allenes through trifunctionalization of 1,3-enynes

Synthesis of Monofluoroalkenes: A Leap Forward

Copper- and Nickel-Catalyzed Cross-Coupling Reaction of Monofluoroalkenes with Tertiary, Secondary, and Primary Alkyl and Aryl Grignard Reagents

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