title: Acid catalyzed alcoholysis of sulfinamides: unusual stereochemistry, kinetics and a question of mechanism involving sulfurane intermediates and their pseudorotation.
abstract: The synthesis of optically active sulfinic acid esters has been accomplished by the acid catalyzed alcoholysis of optically active sulfinamides. Sulfinates are formed in this reaction with a full or predominant inversion of configuration at chiral sulfur or with predominant retention of configuration. The steric course of the reaction depends mainly on the size of the dialkylamido group in the sulfinamides and of the alcohols used as nucleophilic reagents. It has been found that bulky reaction components preferentially form sulfinates with retention of configuration. It has been demonstrated that the stereochemical outcome of the reaction can be changed from inversion to retention and vice versa by adding inorganic salts to the acidic reaction medium. The unusual stereochemistry of this typical bimolecular nucleophilic substitution reaction, as confirmed by kinetic measurements, has been rationalized in terms of the addition-elimination mechanism, A-E, involving sulfuranes as intermediates which undergo pseudorotations.
authors: Department of Heteroorganic Chemistry, Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Łódź, Poland. bogbujni@cbmm.lodz.pl.
authors: Bogdan
authors: B
authors: Bujnicki
authors: Department of Heteroorganic Chemistry, Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Łódź, Poland. draj@cbmm.lodz.pl.
authors: Józef
authors: J
authors: Drabowicz
authors: Department of Heteroorganic Chemistry, Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Łódź, Poland. marmikol@cbmm.lodz.pl.
authors: Marian
authors: M
authors: Mikołajczyk
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D002384:Catalysis; D007700:Kinetics; D015394:Molecular Structure; D012492:Salts; D013237:Stereoisomerism; D013457:Sulfur Compounds / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D000438:Alcohols; D012492:Salts; D013457:Sulfur Compounds