期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 131, 期 46, 页码 16618-+出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja904354g
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资金
- Deutsche Forschungsgemeinschaft (DFG)
- Landesgraduiertenstiftung Baden-Wurttemberg
Though vinyl sulfoxides behave in some respects like a,B-unsaturated carbonyl compounds, the mode of stabilization is significantly different. Interaction of the C=C double bond (acting as a donor) with the electron-withdrawing S=O bond is only possible when the p orbitals of the double bond are collinear with the S-O sigma* orbital. The maximum UV absorbance wavelengths in conformationally constrained substrates bearing an S=O bond collinear with the p orbitals of a C=C double bond are 2-14 nm higher than those in analogous compounds with a roughly orthogonal sulfoxide moiety. Similarly, a lone pair evolving during nucleophilic attack on vinyl sulfoxides is stabilized only if it is oriented anti to a S=O bond, which has significant impact on the stereoselectivities and reaction rates for nucleophitic attack on vinyl sulfoxides. The differing reaction rates of differently configured vinyl sulfoxides were measured in a competition experiment.
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