酮（醛）肟的1,3-氮氢转移反应及其全合成应用研究

In this program, we will explore the 1,3-azaprotio transfer reactions of oximes and non-activated carbon-carbon multiple bonds. Based on the selective coordinative interaction between transitional metal with alkyne or allene functionality, four types of cascade cyclization reactions initiated by 1,3-azaprotio transfer reaction were designed. One objective of the program is to develop one-step methodology to construct an array of ring systems from linear oximes with polyfunctional groups such as alkyne, allene and alkene. The other one is to build new and efficient strategies to synthesize alkaloids such as Nankakurine A, Lycopodine, Securinine and 19-Hydroxyibogamine by using the 1,3-azaprotio transfer reaction as a key reaction.

本项目将探索酮（醛）肟与非活泼碳碳重键的1,3-氮氢转移反应规律及其合成应用。基于过渡金属与炔键/联烯的选择性配位活化作用，发展四种以酮（醛）肟1,3-氮氢转移反应启动的串联成环反应，建立从多官能团（炔、烯、联烯）线型酮（醛）肟分子一步构建不同环系的方法学。同时探索以酮（醛）肟1,3-氮氢转移反应为关键步骤合成生物碱Nankakurine A、Lycopodine、Securinine和19-Hydroxyibogamine的新路线。

项目重点探索过渡金属催化酮（醛）肟1,3-氮氢转移反应、基于1,3-氮氢转移反应启动的串联反应以及部分生物碱合成。内容包括：建立金催化炔基酮肟和联烯基酮肟分子内1,3-氮氢转移反应合成环状硝酮的新方法；建立基于铜、铑试剂催化酮（醛）肟与炔烃分子间1,3-氮氢转移反应的串联反应合成beta-内酰胺和噁唑的方法学；实现铑、钯催化酮（醛）肟的化学发散性合成肟醚、光学纯缩醛；完成生物碱amphimedine、meridine、isocystodamine、cystodytin A-K和segoline A的合成。项目取得一些原创性结果，探索了酮（醛）肟1,3-氮氢转移反应的反应规律及其在杂环化合物和生物碱的合成应用。