三价铑催化N-甲氧基苯甲酰胺与炔丙醇[4+1]环化合成异吲哚啉酮

催化学报 ›› 2017, Vol. 38 ›› Issue (8): 1390-1398.

三价铑催化N-甲氧基苯甲酰胺与炔丙醇[4+1]环化合成异吲哚啉酮

许有伟^a,b, 王芬^a, 于松杰^a, 李兴伟^a

a 中国科学院大连化学物理研究所, 辽宁大连 116023;
b 中国科学院大学, 北京 100049

收稿日期:2017-06-25 修回日期:2017-06-30 出版日期:2017-08-18 发布日期:2017-08-04
通讯作者: 李兴伟
基金资助:
中国科学院大连化学物理研究所；国家自然科学基金（21525208，21472186）.

Rhodium (III)-catalyzed selective access to isoindolinones via formal[4+1]annulation of arylamides and propargyl alcohols

Youwei Xu^a,b, Fen Wang^a, Songjie Yu^a, Xingwei Li^a

a Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
b University of Chinese Academy of Sciences, Beijing 100049, China

Received:2017-06-25 Revised:2017-06-30 Online:2017-08-18 Published:2017-08-04
Supported by:
This work was supported by the Dalian Institute of Chemical Physics, Chinese Academy of Sciences, and the National Natural Science Foundation of China (21525208, 21472186).

摘要/Abstract

摘要：

含N杂环结构广泛存在于具有生物活性的药物或天然产物骨架中.本文开发了一个高效合成含N杂环骨架的方法，这类方法在近年来一直是研究热点.在最近几年，过渡金属催化C-H键活化并随后与不饱和键发生环化反应被认为是一种环境友好且原子经济性高的构建功能化杂环的方法.在这些金属催化的体系中，三价铑催化与炔烃的环化反应体系，被认为是一种高效且有实际意义的合成含N杂环的体系.在这类体系，特别是构建六元环的体系中，炔烃通常作为一个C₂合成子被广泛应用.为了克服这一局限性，Chang课题组和本课题组分别独立报道了通过三价铑催化，炔烃与芳烃硝酮偶联合成吲哚啉化合物，其中炔烃作为一个C₁合成子参与反应.另一方面，本课题组还报道了炔丙醇与吡咯烷苯甲酰胺通过C-H键活化合成1-异色满酮结构，其中由于电子效应，芳基-铑物种对于炔烃的插入是在炔烃的2位.基于上述工作，本文希望通过置换炔丙醇中芳基与烷基的位置，使芳基-铑物种对于炔烃插入的方向发生改变，进而生成联烯中间体，然后发生环化反应生成五元环内酰胺结构.
异吲哚啉酮骨架结构也是一类重要的含N杂环结构，广泛存在于多种天然产物及药物分子中，其合成方法受到广泛关注.尽管此前已有三价铑催化C-H官能团化的方法来构建异吲哚啉酮骨架结构，但通常需要活性极高或易爆的化合物作为反应底物.因此，本文报道一类以简单的炔丙醇与N-甲氧基苯甲酰胺作为起始原料，通过一步[4+1]环化合成异吲哚啉酮骨架结构.本文完成了32个不同官能团取代的异吲哚啉酮骨架结构的合成，反应均可以以中等到良好的收率得到目标产物.另外还进行了放大实验，结果表明可以以克级规模制备异吲哚啉酮化合物，反应剩余的Ag₂CO₃以及生成的单质银可以回收（收率78%）.总之，我们将N-甲氧基苯甲酰胺与炔丙醇在三价铑催化作用下通过C-H键活化的方法环化高效合成N-取代的异吲哚啉酮骨架结构，且该骨架结构含有一个手性中心.催化体系温和，官能团容忍度好.

关键词: 铑, 碳氢活化, [4+1]环化, 炔丙醇, 异吲哚啉酮

Abstract:

A mild and efficient oxidative synthesis of isoindolinones has been realized by Rh(Ⅲ)-catalyzed C-H activation of benzamides and[4 + 1] coupling with propargyl alcohols. This coupling system proceeds with broad substrate scope and mild conditions and provides a new approach to access the useful skeleton of γ-lactams with a stereogenic center.

Key words: Rhodium, C-H activation, [4+1]annulation, Propargyl alcohol, Isoindolinones

许有伟, 王芬, 于松杰, 李兴伟. 三价铑催化N-甲氧基苯甲酰胺与炔丙醇[4+1]环化合成异吲哚啉酮[J]. 催化学报, 2017, 38(8): 1390-1398.

Youwei Xu, Fen Wang, Songjie Yu, Xingwei Li. Rhodium (III)-catalyzed selective access to isoindolinones via formal[4+1]annulation of arylamides and propargyl alcohols[J]. Chinese Journal of Catalysis, 2017, 38(8): 1390-1398.

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