The hetero-Diels-Alder addition of sulfur dioxide: The pseudo-chair conformation of a 4,5-dialkylsultine

Even unsubstituted butadiene adds to sulfur dioxide in the hetero-Diels Alder mode more rapidly than in the chelotropic mode. The sultine can be observed in equilibrium with the diene and the sulfur dioxide only at low temperature and in the presence of CF3COOH. Crystals of 4,5-dialkyl-sultine resulting from the SO2 addition to 1,2 -dimethylidenecyclohexane have been obtained at -100degreesC and analyzed by X-ray diffraction. Quantum chemical calculations have shown that hyperconjugative interactions within the sulfinyl moiety are responsible for the anomeric effects observed in sultines that prefer pseudo-chair conformations with pseudo-axial S=O bonds.


Published in:
Chemistry-a European Journal, 9, 20, 4911-4915
Year:
2003
ISSN:
0947-6539
Keywords:
Note:
BCH, Swiss Inst Technol, Inst Mol & Biol Chem, CH-1015 Lausanne, Switzerland. Univ Oviedo, Dept Quim Fis & Analit, Lab Quim Computac, E-33071 Oviedo, Principado Astu, Spain.
Laboratories:




 Record created 2005-11-09, last modified 2018-03-17


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