Organic synthesis of functional polycyclic compounds with ynolates

2016 Fiscal Year Final Research Report

• Project/Area Number: 26293004
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Partial Multi-year Fund
• Section: 一般
• Research Field: Chemical pharmacy
• Research Institution: Kyushu University
• Principal Investigator: SHINDO MITSURU 九州大学, 先導物質化学研究所, 教授 (40226345)
• Project Period (FY): 2014-04-01 – 2017-03-31
• Keywords: 有機化学 / 多環化合物 / フローリアクター / イノラート / トリプチセン / 全合成 / アルカロイド

Outline of Final Research Achievements

We developed the novel one-pot synthetic method of substituted triptycenes by the reaction of ynolates and arynes. This four-step process involves three cycloadditions and electrocyclic ring opening of the strained Dewar anthracene. Each of the three related but structurally distinct classes of nucleophiles (ynolate, enolate, and anthracenolate) reacts with o-benzyne in the same predictable manner controlled by chelation and negative hyperconjugation. The resulting functionalized C3-symmetrical triptycenes hold promise in the design of functional materials.
The first heterogeneously catalyzed oxidative dehydrogenative homo- and cross-coupling of aryl amines, giving biarylamines, was developed.
Asymmetric total synthesis of (-)-stemonamine was achieved by using ynolate-initiated [2+2]cycloaddition-Dieckmann condensation as a key step.

Free Research Field

有機合成化学