Stereoselective synthesis of mono- and di-substituted dehydroamino acids and its application to the natural product synthesis and chemical biology.

2016 Fiscal Year Final Research Report

• Project/Area Number: 25282233
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Partial Multi-year Fund
• Section: 一般
• Research Field: Biomolecular chemistry
• Research Institution: Osaka City University
• Principal Investigator: SHINADA Tetsuro 大阪市立大学, 大学院理学研究科, 教授 (30271513)
• Project Period (FY): 2013-04-01 – 2017-03-31
• Keywords: デヒドロアミノ酸 / 立体選択的合成 / 天然物合成

Outline of Final Research Achievements

Dehydroamino acid (Dhaa) is a useful tool in the research area of amino acid and peptide chemistry. In this study, we examined the stereoselective synthesis of monosubstituted E-Dhaas and disubstituted Dhaas in which the stereocontrolled syntheses have not been well established yet. We designed a new (diphenylphosphono)glycine to solve the synthetic problems. Various E-Dhaas were prepared with high stereoselectivities using the designed reagent and reaction conditions (additives and bases). The stereoselective synthesis of disubstituted Dhaas were achieved by using the new reagent, (diphenylphosphono)glycine, as a common synthetic precursor. Dehydroisoleucine was prepared by a series of sequential reactions: i) E-selective olefination, ii) Z-selective iodination, and ii) Negishi cross-coupling reaction. The above new method is successfully applied to the stereoselective synthesis of phomopsin A side chain containing dehydroisoleucine and dehydroaspartic acid.

Free Research Field

天然物化学