Development of new transforming reaction using New Mitsunobu reaction and deracemization

利用新光延反应和去消旋反应开发新的转化反应

• 批准号: 17590026
• 负责人: TSUNODA Tetsuto
• 金额: $ 2.3万
• 依托单位: Tokushima Bunri University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2005
• 资助国家: 日本
• 起止时间: 2005 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-17590026/
• 关键词: Mitsunobu Reaction; Dios group; antimycin; asymmetric reaction; aza-Claisen rearrangement; aldol reaction; pigment; aphid; 光延試薬; CMBP; CMMP; Witting型試薬; ゲラニルスルホン; 炭素求核剤; 窒素求核剤

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.

合成了 2-(1,3-二氧杂-2-基)乙基磺酰基 (Dios) 氯化物并用作新型多功能胺磺化剂。伯胺和仲胺很容易用 Dios 氯化物磺化，收率极高。 N-未取代和N-单取代二异酰胺、活化胺在新的Mitsunobu 条件下利用(氰基亚甲基)三丁基正膦(CMBP) 得到令人满意的烷基化。 Dios 基团在碱性和还原条件下非常稳定，并通过在热三氟乙酸水溶液中加热而被除去。从链霉菌属中分离出抗霉素 A (AA) 家族。具有显着的生物活性，如抗真菌、杀虫和抗癌，以及对泛醇细胞色素c氧化还原酶的抑制活性。我们首次高效合成了(+)-AA_9，这是第一个具有芳香族8-酰基残基的抗霉素。Uroleuconaphins A1和B1是从Uroleucon nigrotuberculatum O.中分离出来的红色素，通过单晶确定了它们的结构对它们进行 X 射线分析。

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专利权

• 发表时间: 2018