Design and Synthesis of Chiral Oxathiozinone Scaffolds: Efficient Synthesis of Hindered Enantiopure Sulfinamides and Sulfinyl Ketimines

Abstract

Ist das S‐O? Die im Titel bezeichneten Molekülgerüste verfügen über eine hoch aktive und ausreichend differenzierte S‐O‐Bindung für die effiziente Synthese enantiomerenreiner Sulfinamide. Die beschriebene Methode ist praktisch und umweltverträglich und könnte als Grundlage für ein ökonomisches kommerzielles Verfahren zur Herstellung sperriger Sulfinamide dienen.

Application of Chiral Sulfinamides into Formation and Reduction of Sulfinylketimines to Obtain Valuable α‐Chiral Primary Amines

“…[29] In 2013 Han et al developed a new methodology to access highly sterically hindered sulfinylketimines. [30] They compared the effect of the substituent on the sulfinyl group and have shown that 2,4,6-triisopropylphenyl gave the best diastereoselectivity in the reduction reaction (Scheme 22).…”

Chiral Brønsted acid catalyzed asymmetric oxidation of N‐acyl sulfenamide by H2O2: An efficient approach to obtaining chiral N‐acyl sulfinamide

“…Up to now, chiral sulfinamides were mainly obtained by the nucleophilic substitution reaction between amines and chiral auxiliary agents containing sulfoxide groups (S=O) and leaving groups such as mercapto 11,12 and alkoxy. [13][14][15] Of course, the amount of chiral auxiliaries was equivalent or even excessive in this strategy; what is more, the amines were required to have strong nucleophilicity and the chiral adjuvant needed to have sufficient steric hindrance. In addition to poor atom economy and harsh reaction conditions, this strategy also reflected the lack of universality of the substrate.…”

“…In addition to poor atom economy and harsh reaction conditions, this strategy also reflected the lack of universality of the substrate. [11][12][13][14][15] Therefore, it is of great significance to develop asymmetric catalytic methods with high atom economy to prepare chiral sulfenamides that are difficult to obtain by traditional methods (Scheme 1).…”

“…Compared with its important functional properties, the synthetic method of chiral sulfenamide is obviously restricted, especially when it is examined with the concept of green chemistry. Up to now, chiral sulfinamides were mainly obtained by the nucleophilic substitution reaction between amines and chiral auxiliary agents containing sulfoxide groups (S=O) and leaving groups such as mercapto 11,12 and alkoxy 13–15 . Of course, the amount of chiral auxiliaries was equivalent or even excessive in this strategy; what is more, the amines were required to have strong nucleophilicity and the chiral adjuvant needed to have sufficient steric hindrance.…”

“…Of course, the amount of chiral auxiliaries was equivalent or even excessive in this strategy; what is more, the amines were required to have strong nucleophilicity and the chiral adjuvant needed to have sufficient steric hindrance. In addition to poor atom economy and harsh reaction conditions, this strategy also reflected the lack of universality of the substrate 11–15 . Therefore, it is of great significance to develop asymmetric catalytic methods with high atom economy to prepare chiral sulfenamides that are difficult to obtain by traditional methods (Scheme 1).…”