α-Bromo-α,α-difluoroallyl derivatives as synthetic intermediate: Nucleophilic substitution of α-bromo-α,α-difluoroallyl derivatives in the presence of palladium catalysts

Chemical and Pharmaceutical Bulletin

Volumn 48, Issue 6, 2000, Pages 885-888

  Kirihara, Masayuki ^a   Takuwa, Tomofumi ^a   Okumura, Maiko ^a   Wakikawa, Takahiro ^a   Takahata, Hiroki ^a   Momose, Takefumi ^a   Takeuchi, Yoshio ^a   Nemoto, Hideo ^a  

^a UNIVERSITY OF TOYAMA   (Japan)

Author keywords

3 bromo 3,3 difluoropropene; Difluoroallyl palladium; bromo , difluoroallyl derivative

Indexed keywords

ALKENE DERIVATIVE; ALLYL COMPOUND; PALLADIUM;

ARTICLE; BROMINATION; CATALYSIS; CATALYST; CHEMICAL ANALYSIS; CHEMICAL REACTION; REACTION ANALYSIS; SYNTHESIS;

EID: 0033920401     PISSN: 00092363     EISSN: None     Source Type: Journal    
DOI: 10.1248/cpb.48.885     Document Type: Article

References (17)

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14. A similar selectivity was observed during the radical bromination of 1,1-difluoro-2-phenylthio-1-propene; Jeong I. H., Kim M. S., Kim B. T., Synth. Commun., 29, 235-241 (1999).
15. Although the fluorine atom can stabilize an α-carboradical, its stabilizing effect is very low; Smart B. E., "Organofluorine Chemistry: Principles and Commercial Applications," ed. by Banks R. E., Smart B. E., Tatlow J. C., Plenum Press, New York, 1994, pp. 57-88. The steric effect might play an important role in the radical bromination of 2.
16. We also synthesized methyl 2-aceto-5-bromo-5,5-difluoro-2-methylpent-3-enoate (1d) by the radical bromination of 2b, and confirmed that 1d exclusively reacted with nucleophiles at the α-position to afford the 1,3-disubstituted BDFP (13, 14) in the presence of the palladium catalyst. However, we could not obtain a pure sample of them (1d, 13, 14) due to their instability (Chart 10). (formula presented)
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