Journal article
Synthesis of fluorinated 1,2,3-butatrienes from .alpha.-halovinyl organometallic reagents
Journal of the American Chemical Society, Vol.115(13), pp.5430-5439
06/01/1993
DOI: 10.1021/ja00066a011
Abstract
The thermal stability and dimerization reaction of fluorinated α-halovinyl zinc and copper reagents, RR′C=CYM (Y = F, Cl, Br; M = ZnX, Cu), have been explored in detail. Dimerization of these vinyl carbenoids to butatrienes occurred when R was an aromatic (C6H5 or C6F5) and R′ was a perfluoroalkyl group (CF3, C2F5, C3F7). The role of the α-halogen was determined: the α-F vinyl copper reagent (R = C6H5, R′ = CF3) decomposed by oxidative dimerization to 1,3-dienes while the α-Br and -Cl copper reagents dimerized to butatrienes. The fluorinated butatrienes prepared in this study, (E)- and (Z)-R1R2C=C=C=CR1R2 (R1 = CF3, R2 = C6H5; R1 = C2F5, R2 = C6H5; R1 = n-C3F7, R2 = C6H5; R1 = CF3, R2 = C6F5) are available on a multigram scale and readily obtained with high isomeric purity. The geometry of one member of each isomeric pair of butatrienes was characterized by X-ray crystallography. The mechanism of the dimerization reaction has been determined to be a nucleophilic displacement/α-elimination process. Diels-Alder (1,2-addition), bromination (1,2-addition), and isomerization reactions are described.
Details
- Title: Subtitle
- Synthesis of fluorinated 1,2,3-butatrienes from .alpha.-halovinyl organometallic reagents
- Creators
- Peter A MorkenPatrick C BachandDale C SwensonDonald J Burton
- Resource Type
- Journal article
- Publication Details
- Journal of the American Chemical Society, Vol.115(13), pp.5430-5439
- Publisher
- American Chemical Society
- DOI
- 10.1021/ja00066a011
- ISSN
- 0002-7863
- eISSN
- 1520-5126
- Language
- English
- Date published
- 06/01/1993
- Academic Unit
- Chemistry
- Record Identifier
- 9984622746702771
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