铜催化的烯丙醇自由基胺化/1,2-碳迁移串联反应:一步构建含α-季碳中心的β-胺基酮

doi:10.1016/S1872-2067(17)62915-2

催化学报 ›› 2018, Vol. 39 ›› Issue (1): 138-145.DOI: 10.1016/S1872-2067(17)62915-2

铜催化的烯丙醇自由基胺化/1,2-碳迁移串联反应:一步构建含α-季碳中心的β-胺基酮

孙佳琼, 郑光范, 付永梅, 张乔, 王义敏, 张茜, 李燕, 张前

东北师范大学化学学院, 吉林省有机功能分子设计与合成重点实验室, 吉林长春 130024

收稿日期:2017-09-04 修回日期:2017-09-15 出版日期:2018-01-18 发布日期:2018-01-19
通讯作者: 李燕, 张前
基金资助:
国家自然科学基金（21372041）；长白山学者奖励计划；中央高校基本科研业务费专项资金（2412016KJ006）.

Copper-catalyzed tandem radical amination/1, 2-carbon migration of allylic alcohols: Direct access to α-quaternary-β-amino ketones

Jiaqiong Sun, Guangfan Zheng, Yongmei Fu, Qiao Zhang, Yimin Wang, Qian Zhang, Yan Li, Qian Zhang

Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Faculty of Chemistry, Northeast Normal University, Changchun 130024, Jilin, China

Received:2017-09-04 Revised:2017-09-15 Online:2018-01-18 Published:2018-01-19
Contact: 10.1016/S1872-2067(17)62915-2
Supported by:
This work was supported by the National Natural Science Foundation of China (21372041), Changbai Mountain Scholarship Program, and the Fundamental Research Funds for the Central Universities (2412016KJ006).

摘要/Abstract

摘要：

烯丙醇类化合物是非常重要的有机合成砌块.近年来，自由基或阳离子对烯丙醇类化合物的加成引发的1，2-碳迁移反应迅速发展，被认为是合成含α-季碳中心的β-羰基化合物最有效的策略之一.目前，烯丙醇的官能团化/1，2-碳迁移反应取得了很好的成果，各种官能团化反应，比如卤化、三氟甲基化、硫化、膦化和芳基化等，已经顺利实现.但是，烯丙醇类化合物的胺化/1，2-碳迁移串联反应研究较少.这可能是由于竞争的亲核胺化反应存在导致的.因此，发展烯丙醇类化合物的胺化串联反应值得期待.我们及其他课题组以N-氟代双苯磺酰亚胺（NFSI）作为有效的自由基氮源，实现了烯烃或炔烃的自由基胺化官能团化反应.研究表明，在铜催化温和条件下即可生成金属稳定的氮中心自由基物种.据此，我们认为，在温和条件下有效产生氮中心自由基是实现烯丙醇自由基胺化/1，2-碳迁移串联反应的关键.在前期工作基础上，本文利用NFSI及其衍生物作为有效的自由基胺化试剂，实现了铜催化烯丙醇类化合物的自由基胺化/1，2-碳迁移串联反应，直接构建重要的含α-季碳中心的β-胺基酮骨架.
本文合成了24个不同官能团取代的β-胺基酮衍生物.反应中芳环上取代基的电子效应和空间效应表现并不明显.当芳基对位连有卤素、烷氧基、芳基、烷基时，或者邻位和间位甲基取代的1-（1-芳基烯基）环丁醇均可以与NFSI顺利反应，以中等至较高的产率得到相应的含α-季碳中心的β-胺基酮.氧杂环丁醇、取代的环丁醇类化合物，5元、6元及非环状的苯基烯丙醇类化合物均适用于该反应，生成相应的目标化合物.同时，我们也扩展了胺化试剂的范围，除NFSI衍生物外，单取代的NFHSO₂Ph类型氮源也可以有效发生自由基胺化/1，2-碳迁移串联反应，生成目标产物.另外，扩大反应物的量至5mmol，反应不受影响，仍能以90%的产率生成β-胺基酮衍生物.最后，通过控制实验捕捉到反应中生成的苄基自由基中间体，表明该反应经历氮中心自由基对烯丙醇烯烃双键的区域选择性加成引发的1，2-碳迁移串联反应.
总之，本文以N-F试剂作为自由基胺化试剂，利用铜催化体系发展了烯丙醇类化合物的自由基胺化/1，2-碳迁移串联反应，一步合成了重要的β-胺基酮类化合物.该反应条件温和，底物适用范围宽泛，官能团兼容性较好，合成了一系列链状、环状及螺环的含有α-季碳中心的β-胺基酮衍生物.据我们所知，这是首例将NHFSO₂Ph类型N-F试剂作为自由基氮源的反应.

关键词: 烯丙醇, 氮中心自由基, 1,2-碳迁移反应, 含α-季碳中心的β-胺基酮, N-F试剂

Abstract:

A novel nitrogen-centered radical-induced 1,2-carbon migration reaction of allylic alcohols has been developed. This method provides easy access to a variety of α-quaternary-β-amino ketones under mild reaction conditions. The reaction has a wide substrate scope and operational simplicity. Mechanistic studies suggest that 1,2-carbon migration is induced by regioselective nitrogen-centered radical addition to the alkene unit.

Key words: Allylic alcohols, Nitrogen-centered radicals, 1,2-Carbon migration, α-Quaternary-β-amino ketones, N-F regent

孙佳琼, 郑光范, 付永梅, 张乔, 王义敏, 张茜, 李燕, 张前. 铜催化的烯丙醇自由基胺化/1,2-碳迁移串联反应:一步构建含α-季碳中心的β-胺基酮[J]. 催化学报, 2018, 39(1): 138-145.

Jiaqiong Sun, Guangfan Zheng, Yongmei Fu, Qiao Zhang, Yimin Wang, Qian Zhang, Yan Li, Qian Zhang. Copper-catalyzed tandem radical amination/1, 2-carbon migration of allylic alcohols: Direct access to α-quaternary-β-amino ketones[J]. Chinese Journal of Catalysis, 2018, 39(1): 138-145.

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铜催化的烯丙醇自由基胺化/1,2-碳迁移串联反应:一步构建含α-季碳中心的β-胺基酮

Copper-catalyzed tandem radical amination/1, 2-carbon migration of allylic alcohols: Direct access to α-quaternary-β-amino ketones

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