Development of new transforming reaction using New Mitsunobu reaction and deracemization

合成了2-(1，3-二氧杂-2-基)乙磺酰氯(DIOS)，并将其作为一种新型的多胺磺化试剂。伯胺和仲胺在Dios氯化物中以极高的产率非常容易地磺化。在新的Mitsunobu反应条件下，N-未取代和N-单取代二胺类活化胺利用(氰亚甲基)三丁基膦(CMBP)进行了满意的烷基化反应。Dios基团在碱性和还原条件下非常稳定，可在三氟乙酸热水溶液中加热除去。从链霉菌中分离出抗霉素A(AA)家族。具有显著的生物活性，如抗真菌、杀虫和抗癌，以及对泛喹酚-细胞色素c氧化还原酶的抑制活性。我们首次高效地合成了(+)-AA9，这是第一个具有芳香族8-酰基残基的抗菌素。尿亮蛋白A1和B1是从黑色尿白蛋白中分离得到的红色色素，它们的结构通过单晶X-射线分析确定。

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.