Rh(II)催化3-重氮吲哚酮与烯基叠氮的烯化/环化反应合成螺吡咯啉吲哚酮

doi:10.1016/S1872-2067(18)63200-0

催化学报 ›› 2019, Vol. 40 ›› Issue (2): 177-183.DOI: 10.1016/S1872-2067(18)63200-0

Rh(II)催化3-重氮吲哚酮与烯基叠氮的烯化/环化反应合成螺吡咯啉吲哚酮

易如霞^a,b, 钱磊磊^a,b, 万伯顺^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:2018-11-02 修回日期:2018-11-14 出版日期:2019-02-28 发布日期:2019-01-11
通讯作者: 万伯顺
基金资助:
国家自然科学基金（21572225）.

Synthesis of spiropyrrolidine oxindoles through Rh(II)-catalyzed olefination/cyclization of diazooxindoles and vinyl azides

Ruxia Yi^a,b, Leilei Qian^a,b, Boshun Wan^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:2018-11-02 Revised:2018-11-14 Online:2019-02-28 Published:2019-01-11
Contact: 10.1016/S1872-2067(18)63200-0
Supported by:
This work was supported by the National Natural Science Foundation of China (21572225).

摘要/Abstract

摘要：

螺吡咯啉吲哚酮化合物含有两种重要氮杂环，由于其独特的结构骨架和存在于天然产物而被广泛关注.吲哚酮的3位与其它环状化合物以螺环形式结合的结构特点是该结构具有潜在药物活性和合成价值的基础，例如抗癌和抗菌活性，以及在合成新配体和有机催化剂上的应用.目前，尽管合成螺吲哚酮的策略已有1，3-偶极环加成、亲核加成及还原环化等，但是发展简单高效的构建螺吲哚酮化合物的方法仍具有很大的吸引力.
烯基叠氮同时含有叠氮和烯基两个单元，被广泛应用于构建氮杂环.另一方面，重氮化合物被广泛用作偶联环化合成的底物.基于在叠氮化学和杂环合成方面的工作，我们设想利用3-重氮吲哚-2-酮和烯基氮的环化反应构建螺吲哚酮化合物.文献中有关烯基叠氮和重氮化合物反应的报道较少，主要涉及铑催化的环丙烷化和铜催化的环戊烯合成，在这些反应中烯基叠氮作为二元合成子参与反应，而其它类型的反应鲜有报道，因此我们设想利用烯基叠氮作为三元合成子来参与反应成环.在我们开展工作的同时，Katukojvala小组率先发表了铑催化的重氮烯和烯基叠氮的环化反应构建1-吡咯啉.
本文报道了3-重氮吲哚酮和烯基叠氮在铑催化下发生[1+1+3]环化，构建一系列螺吡咯啉吲哚酮化合物.研究从反应条件优化开始，通过对催化剂、原料比、溶剂和温度等参数的筛选，确定了最佳反应条件为1a/2a（1/7），Rh₂（TFA）₄（2.5 mol%），1，2-二氯乙烷（0.1 mol/L），60℃.在标准条件下完成了21个不同基团取代的螺吡咯啉吲哚酮化合物的合成，最高收率可达91%，证实了该反应的普适性.当重氮底物的N原子上不含取代基或取代基为甲基、苄基、苯基、苯甲酰基和磺酰基时，反应均可以顺利发生，其中苯甲酰基和对甲苯磺酰基取代的底物的反应可取得90%以上的收率.对于重氮和烯基叠氮底物的苯环上含有卤素、甲基和甲氧基等取代基时，反应同样可以顺利进行，以中等收率得到对应产物，电子效应对反应效果影响不大，而存在位阻效应时反应收率略有降低.当降低反应温度或缩短反应时间，可以从反应体系中同时分离得到螺吡咯啉吲哚酮和重氮底物3位乙烯基化的产物.进一步实验表明，3-烯基吲哚酮可以在标准条件下与烯基叠氮反应，以中等收率得到模板产物.该对照实验表明3-烯基吲哚酮是反应过程中的关键中间体.该反应条件温和，简单高效，底物适用范围广，为构建具有潜在生物活性的螺吲哚酮骨架提供了新的选择.

关键词: 铑催化剂, 烯基叠氮, 重氮化合物, 螺吡咯啉吲哚酮, 乙烯基化, [1+1+3]环化

Abstract:

A simple and efficient process involving the Rh(Ⅱ)-catalyzed[1+1+3] annulation of diazooxindoles and vinyl azides has been developed for the synthesis of spiropyrrolidine oxindoles with potential biological activity and significant synthetic applications. This process involves a novel rhodium-catalyzed olefination of diazo compounds, followed by annulation with vinyl azides. This method is compatible with a broad range of substrates and affords moderate to good yields under mild reaction conditions.

Key words: Rhodium catalyst, Vinyl azides, Diazo compounds, Spiropyrrolidine oxindoles, Olefination, [1+1+3] annulation

易如霞, 钱磊磊, 万伯顺. Rh(II)催化3-重氮吲哚酮与烯基叠氮的烯化/环化反应合成螺吡咯啉吲哚酮[J]. 催化学报, 2019, 40(2): 177-183.

Ruxia Yi, Leilei Qian, Boshun Wan. Synthesis of spiropyrrolidine oxindoles through Rh(II)-catalyzed olefination/cyclization of diazooxindoles and vinyl azides[J]. Chinese Journal of Catalysis, 2019, 40(2): 177-183.

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Rh(II)催化3-重氮吲哚酮与烯基叠氮的烯化/环化反应合成螺吡咯啉吲哚酮

Synthesis of spiropyrrolidine oxindoles through Rh(II)-catalyzed olefination/cyclization of diazooxindoles and vinyl azides

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