Synthesis and characterization of β-haloalkenyl-λ3- bromanes: Stereoselective markovnikov addition of difluoro(aryl)- λ3-bromane to terminal acetylenes

Masahito Ochiai; Yoshio Nishi; Takeshi Mori; Norihiro Tada; Takashi Suefuji; Hermann J. Frohn

doi:10.1021/ja051690f

Synthesis and characterization of β-haloalkenyl-λ³- bromanes: Stereoselective markovnikov addition of difluoro(aryl)- λ³-bromane to terminal acetylenes

Masahito Ochiai, Yoshio Nishi, Takeshi Mori, Norihiro Tada, Takashi Suefuji, Hermann J. Frohn

Research output: Contribution to journal › Article › peer-review

24 Citations (Scopus)

Abstract

Reported here for the first time are the synthesis, isolation, and characterization of hypervalent β-haloalkenyl-λ³-bromanes. Exposure of terminal alkynes to p-trifluoromethylphenyl(difluoro)-λ³-bromane activated by BF₃-i-Pr₂O resulted in fluoro-λ³-bromanation of the triple bonds in a Markovnikov fashion, yielding (E)-β-fluoroalkenyl-λ³-bromanes stereoselectively in good yields. 5-Chloro-1-pentynes undergo domino λ³-bromanation-chlorine shift-fluorination or λ³-bromanation-chlorine shift-alkyl shift-fluorination reaction, depending on the substituents and afford (E)-β-chloroalkenyl-λ³-bromanes stereoselectively in high yields. The β-chloroalkenyl-λ³-bromanes contain three kinds of halogen atoms, F, Cl, and Br, in the molecule.

Original language	English
Pages (from-to)	10460-10461
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	127
Issue number	30
DOIs	https://doi.org/10.1021/ja051690f
Publication status	Published - Aug 3 2005
Externally published	Yes

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja051690f

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Synthesis and characterization of β-haloalkenyl-λ³- bromanes: Stereoselective markovnikov addition of difluoro(aryl)- λ³-bromane to terminal acetylenes. / Ochiai, Masahito; Nishi, Yoshio; Mori, Takeshi et al.
In: Journal of the American Chemical Society, Vol. 127, No. 30, 03.08.2005, p. 10460-10461.

Research output: Contribution to journal › Article › peer-review

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abstract = "Reported here for the first time are the synthesis, isolation, and characterization of hypervalent β-haloalkenyl-λ3-bromanes. Exposure of terminal alkynes to p-trifluoromethylphenyl(difluoro)-λ3-bromane activated by BF3-i-Pr2O resulted in fluoro-λ3-bromanation of the triple bonds in a Markovnikov fashion, yielding (E)-β-fluoroalkenyl-λ3-bromanes stereoselectively in good yields. 5-Chloro-1-pentynes undergo domino λ3-bromanation-chlorine shift-fluorination or λ3-bromanation-chlorine shift-alkyl shift-fluorination reaction, depending on the substituents and afford (E)-β-chloroalkenyl-λ3-bromanes stereoselectively in high yields. The β-chloroalkenyl-λ3-bromanes contain three kinds of halogen atoms, F, Cl, and Br, in the molecule.",

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AU - Ochiai, Masahito

AU - Nishi, Yoshio

AU - Mori, Takeshi

AU - Tada, Norihiro

AU - Suefuji, Takashi

AU - Frohn, Hermann J.

PY - 2005/8/3

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N2 - Reported here for the first time are the synthesis, isolation, and characterization of hypervalent β-haloalkenyl-λ3-bromanes. Exposure of terminal alkynes to p-trifluoromethylphenyl(difluoro)-λ3-bromane activated by BF3-i-Pr2O resulted in fluoro-λ3-bromanation of the triple bonds in a Markovnikov fashion, yielding (E)-β-fluoroalkenyl-λ3-bromanes stereoselectively in good yields. 5-Chloro-1-pentynes undergo domino λ3-bromanation-chlorine shift-fluorination or λ3-bromanation-chlorine shift-alkyl shift-fluorination reaction, depending on the substituents and afford (E)-β-chloroalkenyl-λ3-bromanes stereoselectively in high yields. The β-chloroalkenyl-λ3-bromanes contain three kinds of halogen atoms, F, Cl, and Br, in the molecule.

AB - Reported here for the first time are the synthesis, isolation, and characterization of hypervalent β-haloalkenyl-λ3-bromanes. Exposure of terminal alkynes to p-trifluoromethylphenyl(difluoro)-λ3-bromane activated by BF3-i-Pr2O resulted in fluoro-λ3-bromanation of the triple bonds in a Markovnikov fashion, yielding (E)-β-fluoroalkenyl-λ3-bromanes stereoselectively in good yields. 5-Chloro-1-pentynes undergo domino λ3-bromanation-chlorine shift-fluorination or λ3-bromanation-chlorine shift-alkyl shift-fluorination reaction, depending on the substituents and afford (E)-β-chloroalkenyl-λ3-bromanes stereoselectively in high yields. The β-chloroalkenyl-λ3-bromanes contain three kinds of halogen atoms, F, Cl, and Br, in the molecule.

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Synthesis and characterization of β-haloalkenyl-λ³- bromanes: Stereoselective markovnikov addition of difluoro(aryl)- λ³-bromane to terminal acetylenes

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