基于惰性C(sp3)-H胺化反应设计合成新型伯胺-硫脲有机催化剂

doi:10.16183/j.cnki.jsjtu.2020.144

上海交通大学学报 ›› 2020, Vol. 54 ›› Issue (12): 1335-1339.doi: 10.16183/j.cnki.jsjtu.2020.144

基于惰性C(sp³)-H胺化反应设计合成新型伯胺-硫脲有机催化剂

练鹏飞, 王训辉, 张书宇()

上海交通大学　化学化工学院，上海　200240

收稿日期:2020-05-22 出版日期:2020-12-01 发布日期:2020-12-31
通讯作者: 张书宇 E-mail:zhangsy16@sjtu.edu.cn
作者简介:练鹏飞(1995-)，男，河南省永城市人，硕士生，主要从事有机合成方法学的研究．
基金资助:
国家自然科学基金(21672145);秦惠君与李政道中国大学生见习进修基金资助项目

Design and Synthesis of a Novel Primary Amine-Thiourea Organocatalyst Based on Unactivated C(sp³)-H Amination Reaction

LIAN Pengfei, WANG Xunhui, ZHANG Shuyu()

School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China

Received:2020-05-22 Online:2020-12-01 Published:2020-12-31
Contact: ZHANG Shuyu E-mail:zhangsy16@sjtu.edu.cn

摘要/Abstract

摘要：

为了将碳氢活化策略应用于新型有机催化剂的合成，将开发的惰性C(sp³)-H胺化方法作为关键步设计合成了新型伯胺-硫脲催化剂．首先，使用以苯丙氨酸为母核的底物，偶氮二甲酸二叔丁酯作为氮源，利用Pd催化的惰性C(sp³)-H胺化方法获得相应的氨基化产物，并经简单转化获得有机催化剂中常见的手性1，2-二胺优势骨架．然后，进一步衍生合成了新型手性伯胺-硫脲双功能有机催化剂，并用核磁共振波谱、高分辨质谱等对其结构进行表征．最后，合成的催化剂还成功应用于催化异丁醛与硝基烯烃的不对称Michael加成反应．由于过渡金属催化的C-H活化具有简洁、高效、原子经济、无需预官能团化等优点，将其应用于小分子催化剂的开发无疑会使得催化剂的合成更为高效，结构更加多样．

关键词: C-H胺化, 伯胺, 硫脲, 有机催化

Abstract:

In order to apply the C-H activation strategy to the synthesis of novel organic catalysts, a novel primary amine-thiourea catalyst is designed and synthesized by using the developed inert C(sp³)-H amination method as a key step. First, using phenylalanine as the substrate and di-tert-butyl-azodicarboxylic acid as the nitrogen source, the corresponding amination products are obtained by employing the Pd-catalyzed inert C(sp³)-H amination method. Next, the chiral skeleton of 1,2-diamine privileged in organocatalysts is obtained by simple conversion. Then, a novel chiral primary amine-thiourea bifunctional organic catalyst is synthesized, whose structure is characterized by nuclear magnetic resonance (NMR) and high resolution mass spectrometry (HRMS). The synthesized catalyst is also successfully applied to the asymmetric Michael addition reaction of isobutyraldehyde with nitroolefins. Due to the advantages of transition metal-catalyzed C-H activation, such as simplicity, high efficiency, high atomic economy, and non pre-functionalization, its application to the development of small molecular catalysts will undoubtedly make the structure of catalyst more diversified and the synthesis process more efficient.

Key words: C-H amination, primary amine, thiourea, organic catalysis

中图分类号:

O621.3

练鹏飞, 王训辉, 张书宇. 基于惰性C(sp³)-H胺化反应设计合成新型伯胺-硫脲有机催化剂[J]. 上海交通大学学报, 2020, 54(12): 1335-1339.

LIAN Pengfei, WANG Xunhui, ZHANG Shuyu. Design and Synthesis of a Novel Primary Amine-Thiourea Organocatalyst Based on Unactivated C(sp³)-H Amination Reaction[J]. Journal of Shanghai Jiao Tong University, 2020, 54(12): 1335-1339.

图/表 2

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基于惰性C(sp³)-H胺化反应设计合成新型伯胺-硫脲有机催化剂

Design and Synthesis of a Novel Primary Amine-Thiourea Organocatalyst Based on Unactivated C(sp³)-H Amination Reaction

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