59203-03-1Relevant academic research and scientific papers
Acid catalyzed alcoholysis of sulfinamides: Unusual stereochemistry, kinetics and a question of mechanism involving sulfurane intermediates and their pseudorotation
Bujnicki, Bogdan,Drabowicz, Jzef,Mikolajczyk, Marian
, p. 2949 - 2972 (2015/09/21)
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.
Asymmetric synthesis of chiral organosulfur compounds using N-sulfinyloxazolidinones
Evans, David A.,Faul, Margaret M.,Colombo, Lino,Bisaha, John J.,Clardy, Jon,Cherry, David
, p. 5977 - 5985 (2007/10/02)
This paper describes a new class of chiral sulfinyl transfer reagents, 4 and 5 (R = aryl, alkyl), which are readily prepared from the oxazolidinones derived from (4R,5S)-norephedrine (HXN) and (4S)-phenylalanine (HXp), respectively. These N-suIfinyloxazolidinone reagents can be synthesized either by sulfinylation-of the metalated oxazolidinones or by oxidation of the derived N-sulfenimides to afford the diastereomeric N-sulfinyloxazolidinones which may be readily purified by chromatography. These sulfinylating agents react with a wide range of nucleophiles such as Grignard reagents, enolates, lithium alkoxides, or metalated amides, with inversion of configuration at the sulfur center to afford the derived chiral sulfoxides, sulfinate esters, and sulfinamides in high yields and enantioselectivities. Competition experiments have established that this family of chiral sulfinylating agents is at least 100 times as reactive as the corresponding menthyl sulfinate esters toward Grignard reagents.
