Development of new transforming reaction using New Mitsunobu reaction and deracemization

合成了2-（1,3-二氧杂甲-2-基）乙基磺酰氯，并将其作为一种新型的多用途胺磺化剂。伯胺和仲胺很容易用二氯甲烷磺化，收率很高。利用（氰乙烯）三丁基磷烷（CMBP），在新的光信条件下进行了n -非取代和n -单取代二氧基酰胺的烷基化反应。Dios基团在碱性和还原性条件下非常稳定，在三氟乙酸热水溶液中加热去除。从Streptomyces sp.中分离到的抗霉素A （antiycin A， AA）家族具有显著的抗真菌、杀虫、抗癌等生物学活性，并具有抑制泛醇-细胞色素c氧化还原酶的活性。我们首次高效合成了(+)-AA_9，这是第一个具有芳香8-酰基残基的抗霉素。尿白细胞素A1和B1是从黑结核尿白细胞中分离出来的红色色素，通过单晶x射线分析确定了它们的结构。

2-(1,3-Dioxa-2-yl)ethylsulfonyl (Dios) chloride was synthesized and used as a new versatile sulfonating agent for amines. Primary and secondary amines were sulfonated very easily in excellent yields with Dios chloride. N-nonsubstituted and N-monosubstituted Dios-amides, activated amines, were alkylated satisfactorily under new Mitsunobu conditions utilizing (cyanomethylene) tributylphosphorane (CMBP). The Dios group was very stable under basic and reductive conditions and was removed by heating in a hot aqueous solution of trifluoroacetic acid.The antimycin A (AA) family isolated from Streptomyces sp. possesses significant biological activities, such as antifungal, insecticidal, and anticancer, as well as an inhibitory activity against ubiquinol-cytochrome c oxidoreductase. We performed the first and efficient synthesis of (+)-AA_9, which is the first antimycin having an aromatic 8-acyl residue.Uroleuconaphins A1 and B1 are red pigments isolated from Uroleucon nigrotuberculatum O., and their structures were determined by a single crystal X-ray analysis of them.