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.
Keywords: ab initio calculations ; conformation analysis ; cycloadditions ; heterocycles ; sulfur ; Cheletropic additions ; quantum calculations ; competition ; 1 ; 3-dienes ; 2 ; 5-dihydrothiophene-1 ; 1-dioxides ; stereoselectivity ; regioselectivity ; buta-1 ; 3-dienes ; sulfolenes ; sultines ; 2 ; 3-dienes
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.
Record created on 2005-11-09, modified on 2016-08-08