Construction of quaternary stereogenic carbon centers via central-axial-central chirality transfer

2014 Fiscal Year Final Research Report

• Project/Area Number: 24590016
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Chemical pharmacy
• Research Institution: University of Shizuoka
• Principal Investigator: EGI Masahiro 静岡県立大学, 薬学部, 准教授 (80363901)
• Project Period (FY): 2012-04-01 – 2015-03-31
• Keywords: アレン / インデン / シグマトロピー転位 / 天然物合成 / 不斉転写 / プロパルギルアルコール / 分子内環化 / 有機合成化学

Outline of Final Research Achievements

I have developed a new method for the preparation of optically active tetrasubstituted allenes. In the presence of AgOTf, the reaction of tertiary propargyl alcohols with an ynamide, followed by the [3,3]-sigmatropic rearrangement, proceeded under mild conditions to afford tetrasubstituted allenes. The central chirality of propargyl alcohols was completely transferred into the axial chirality of allenes.
The platinum-catalyzed intramolecular cyclization of the formed allenes provided polysubstituted indene derivatives, bearing a quaternary stereogenic carbon center, in high yields and with the axial-to-central chirality transfer. Moreover, the reaction using the combination of platinum catalysts and AgOTf allowed for the formation of multisubstituted unsaturated lactones.
This methodology was applied to the synthetic study of bioactive natural products.

Free Research Field

医歯薬学