87716-93-6Relevant academic research and scientific papers
SYNTHESIS OF 3-SUBSTITUTED trans-2-OXADECALINS AND 1-SUBSTITUTED trans-2-OXAHYDRINDANES
Volynskii, N. P.,Alikhanova, O. L.
, p. 1652 - 1663 (2007/10/02)
A study was carried out of the intramolecular cyclization of trans-1-methoxymethyl-2-(1-hydroxyalkyl)cyclohexanes and trans-1-methoxymethyl-2-(2-hydroxyalkyl)cyclohexanes by the action of acid chlorides of phosphorous, sulfurous and p-toluenesulfonic acid
Intermolecular Stereoselective Pummerer Reactions of 4-(p-Chlorophenyl)thiane 1-Oxides and trans-1-Thiadecalin 1-Oxides and 2-Thiadecalin 2-Oxides with Acetic Anhydride
Oae, Shigeru,Itoh, Osamu,Numata, Tatsuo,Yoshimura, Toshiaki
, p. 270 - 279 (2007/10/02)
The Pummerer reactions of cnformationally fixed 4-(p-chlorophenyl)thiane 1-oxides and trans-1-thiadecalin 1-oxides and trans-2-thiadecalin 2-oxides with acetic anhydride are either stereoselective or stereospecific, both in the absence and in the presence of a scavenger of acetic acid formed, such as dicyclohexylcarbodiimide (DCC) or 2,6-lutidine.However, the 18O-tracer experiments with the 18O-labeled sulfoxide revealed the reaction to be an intermolecular rearrangement, while the kinetic experiment with α-deuterated 4-(p-chlorophenyl)thiane 1-oxides gave sizable values of kinetic isotope effect, i.e., 2.8 for the cis isomer and 3.4 for the trans isomer.In the reaction of 4-arylthiane 1-oxides with acetic anhydride, the thermodynamically controlled product is axial 2-acetoxy-4-(p-chlorophenyl)thiane while the kinetically controlled product is the equatorial isomer which is formed in the presence of the acid scavenger, DCC.In the Pummerer reaction of the thiadecalins S-oxides the equatorial α-acetoxy sulfides are the preferential products, however, the isomer preference is more pronounced in the reaction with DCC.These observations, along with other pertinent data seem to suggest that the rate-determining step in the Pummerer reaction of these simple heterocyclic sulfoxides is E2 elimination of acetic acid from the acetoxysulfonium intermediates.
