Synthesis of 2-Phenylated 1,1-difluoro-1,3-enynes via Alkynylation of β,β-Difluoro-α-phenylvinylstannane

Han, Seung Yeon; Choi, Ji Hoon; Hwang, Ji Hye; Jeong, Ilgyu

doi:10.5012/bkcs.2010.31.5.1121

Cited by 11 publications

(2 citation statements)

References 28 publications

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“…Ichikawa et al synthesized 2-alkylated 1,1-difluoro-1,3-enynes via the coupling reaction of 1-alkyl-2,2-difluorovinylboranes with 1-halo-1-alkynes in the presence of cuprous iodides, but 2-phenylated 1,1-difluoro-1,3-enynes can't be prepared from this method [21]. Recently, we reported an efficient method for the preparation of 2-phenyl-1,1-difluoro-1,3-enynes from the crosscoupling reaction of 2,2-difluoro-1-phenylethenylstannane with alkynyl iodides in the presence of catalytic amount of Pd(PPh 3 ) 4 and CuI [22]. However, the previous methods still have some limitations such as tedius procedure for the synthesis of starting material and lack of generality.…”

Section: Introductionmentioning

confidence: 97%

Synthesis of 2-aryl-1,1-difluoro-1,3-enynes via consecutive cross-coupling reactions of 2,2-difluoro-1-iodoethenyl p-toluenesulfonate

Kim¹,

Jeong²,

Jeon³

et al. 2014

Journal of Fluorine Chemistry

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Section: Introductionmentioning

confidence: 97%

Synthesis of 2-aryl-1,1-difluoro-1,3-enynes via consecutive cross-coupling reactions of 2,2-difluoro-1-iodoethenyl p-toluenesulfonate

Kim¹,

Jeong²,

Jeon³

et al. 2014

Journal of Fluorine Chemistry

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“…22 Alkenylation and alkynylation of 2,2-difluoro-1-phenylethenylstannane provided the corresponding 1,1-difluoro-1,3-butadienes 23 and 1,1-difluoro-1,3-enynes. 24 Recently, efficient synthesis of 2,2-diaryl-1,1-difluoroethenes can be achieved by consecutive cross-coupling reactions of 2,2-difluoro-1-tributylstannylethenyl ptoluenesulfonate. 25 However, a general preparation of 1-aryl-2,2-difluoroethenylstannane which is a better coupling partner of arylation as compared to 1-aryl-2,2-difluoroethenyltosylate 25 has not been reported in the previous liternature.…”

Section: 17mentioning

confidence: 99%

Preparation of 2,2-Difluoro-1-arylethenylstannane as a Precursor of 1,1-Diaryl-2,2-difluoroethenes

Lee¹,

Jeon

Jeon³

et al. 2012

Bulletin of the Korean Chemical Society

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gem-Difluoroolefins have attracted much attention because they show chemical reactivities toward nucleophiles 1,2 and are useful intermediate for the synthesis of fluorinated organic compounds via addition-elimination reaction.3 They are also important class of potential mechanism-based inhibitors 4 and have been known to behave as a bioisostere for carbonyl group. 5 The synthesis of gem-difluoroolefins can be mainly achieved by two generalized methods such as Wittig and related reaction, and metalation and related chemistry.6,7 However, Wittig methodology was not suitable for the preparation of 1,1-diaryl-2,2-difluoroethenes because of the poor reactivity of the diaryl ketones.8-11 One straightforward route to 1,1-diaryl-2,2-difluoroethenes is to use 2,2-difluoroethenylmetal reagents. Among these reagents, one of the promising precursors to gem-difluoroolefins is 2,2-difluoroethenylstannane reagents which can be utilized as cross-coupling reaction at stannyl site. Although numerous methods for the preparation of 2,2-difluoroethenylmetal reagents have been well documented in the previous literatures, 12-15 methods for the preparation of 2,2-difluoroethenylstannane reagents have been quite limited, in which 1,1-diaryl-2,2-difluoroethenes can be easily prepared by the Stille cross-coupling reaction. Percy et al. reported a method for the synthesis of 2,2-difluoro-1-tributylstannylethenyl diethylcarbamate from the reaction of 2,2-difluoro-1-lithioethenyl diethylcarbamate with tributylstannyl chloride. 16,172,2-Difluoro-1-tributylstannylethenyl ethers were prepared in a similar manner and their cross-coupling with aryl iodides, followed by cleavage of ether linkage provided difluoromethyl ketones.18,19 Burton et al. synthesized 2,2-difluoroethenylstannane from the reaction of 2,2-difluoroethenyltriethylsilane with tributylstannyl chloride in the presence of KF.20 He also prepared 2,2-difluoro-1-bromoethenylstannane from the reaction of 1,1-dibromo-2,2-difluoroethene with tributyltin chloride in the presence of Zn metal. 21 We reported a method for the preparation of 2,2-difluoro-1-phenylethenylstannane from the stannylation of sulfonyl group in 2,2-difluoro-1-phenylethenylsulfone and its arylation to give 1,1-diaryl-2,2-difluoroethenes.22 Alkenylation and alkynylation of 2,2-difluoro-1-phenylethenylstannane provided the corresponding 1,1-difluoro-1,3-butadienes 23 and 1,1-difluoro-1,3-enynes.24 Recently, efficient synthesis of 2,2-diaryl-1,1-difluoroethenes can be achieved by consecutive cross-coupling reactions of 2,2-difluoro-1-tributylstannylethenyl ptoluenesulfonate.25 However, a general preparation of 1-aryl-2,2-difluoroethenylstannane which is a better coupling partner of arylation as compared to 1-aryl-2,2-difluoroethenyltosylate 25 has not been reported in the previous liternature. Herein, we wish to report a general method for the preparation of 1-aryl-2,2-difluoroethenylstannane which should be a nice precursor to 1,1-diaryl-2,2-difluoroethenes.2,2-Difluoro-1-tributylstannylethenyl p-toluenesulfonate (1) w...

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Formation of Alkenes by Metal‐promoted Coupling Reactions

Larock

Zeni

2018

Comprehensive Organic Transformations

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Alkali Metal Reagents Grignard Reagents Boron Reagents Aluminum Reagents Indium Reagents Thallium Reagents Silicon Reagents Germanium Reagents Tin Reagents Bismuth Reagents Arsenic Reagents Sulfur Reagents Selenium Reagents Tellurium Reagents Titanium Reagents Zirconium Reagents Vanadium Reagents Molybdenum Reagents Manganese Reagents Iron Reagents Ruthenium Reagents Cobalt Reagents Nickel Reagents Palladium Reagents Copper Reagents Silver Reagents Zinc Reagents Mercury Reagents Olefin Metathesis

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Synthesis of 2-Phenylated 1,1-difluoro-1,3-enynes via Alkynylation of β,β-Difluoro-α-phenylvinylstannane

Cited by 11 publications

References 28 publications

Synthesis of 2-aryl-1,1-difluoro-1,3-enynes via consecutive cross-coupling reactions of 2,2-difluoro-1-iodoethenyl p-toluenesulfonate

Synthesis of 2-aryl-1,1-difluoro-1,3-enynes via consecutive cross-coupling reactions of 2,2-difluoro-1-iodoethenyl p-toluenesulfonate

Preparation of 2,2-Difluoro-1-arylethenylstannane as a Precursor of 1,1-Diaryl-2,2-difluoroethenes

Formation of Alkenes by Metal‐promoted Coupling Reactions

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