Development of Novel Stereoselective Molecular Transformations based on Ylide Activation, and Their Synthetic Applications

2017 Fiscal Year Final Research Report

• Project/Area Number: 15K05497
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Shinshu University
• Principal Investigator: SUGA Hiroyuki 信州大学, 学術研究院工学系, 教授 (60211299)
• Co-Investigator(Renkei-kenkyūsha): TODA Yasunori 信州大学, 学術研究院工学系, 助教 (60758978)
• Project Period (FY): 2015-04-01 – 2018-03-31
• Keywords: 付加環化 / ジアゾ化合物 / キラルルイス酸 / エナンチオ選択性 / 二成分触媒 / カルボニルイリド / オキシドピリリウムイリド

Outline of Final Research Achievements

Stereoselective syntheses of optically active 6,8-dihydroxy-, 6,7,8-trihydroxy-, and 1,6,7,8-tetrahydroxyindolizidines have been investigated using the cycloadducts obtained by stereoselective asymmetric 1,3-dipolar cycloaddition reactions between 3-(2-alkenoyl)-2-oxazolidinones and cyclic carbonyl ylides, which were generated from N-diazoacetyl-2-pyrrolidinones, using dual catalytic systems. The first asymmetric alcohol addition reactions to cyclic carbonyl ylides generated from α-alkyl-3-(diazoacetyl)-2-oxazolidinones using a dual catalytic system, which consists of dirhodium tetrapivalate and a chiral Lewis acid, have been developed. The unique heterobicyclic products having quaternary heteroatom-substituted carbon were easily hydrolyzed to oxazolidine-2,4-diones, which could be converted to synthetically useful chiral oxazolidin-2-ones. An efficient method for the generation of an oxidopyrylium ylide from a 2H-pyran-3(6H)-one derivative using a Pd catalyst has been developed.

Free Research Field

有機合成化学