底物与条件控制苯胺与丙烯醛/烯酮的化学选择性偶联反应

引用本文: 周旭凯, 孙佳琼, 李兴伟. 底物与条件控制苯胺与丙烯醛/烯酮的化学选择性偶联反应[J]. 催化学报, 2018, 39(11): 1782-1791. doi: 10.1016/S1872-2067(18)63134-1 shu

Citation: Xukai Zhou, Jiaqiong Sun, Xingwei Li. Chemo-selective couplings of anilines and acroleins/enones under substrate control and condition control[J]. Chinese Journal of Catalysis, 2018, 39(11): 1782-1791. doi: 10.1016/S1872-2067(18)63134-1 shu

底物与条件控制苯胺与丙烯醛/烯酮的化学选择性偶联反应

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
基金项目:
国家自然科学基金（21525208，21472186）；中国科学院大连化学物理研究所甲醇转化与煤代油专项基金.

摘要: 金属催化碳氢键活化已经成为制备高附加值有机化合物的一类高效方法，由于碳氢键广泛存在，所以对它们进行化学、区域、立体选择性的活化作为一大挑战已经被人们日益所关注，然而氧化还原选择性控制的研究十分少见.通常而言，有机氧化还原反应定义为得失氢氧原子，例如消除氢负离子为氧化反应，而失去一个质子则为中性反应.在已有的研究中单独的氧化、还原反应已经被广泛研究，而且被大量用于医药合成、精细化工品的制备以及各类先进材料的生成.但是在同一反应体系下同时调控三种氧化态的研究目前未见报道，因此发展这类选择性控制的反应十分重要.我们此前已经实现了Rh（Ⅲ）/Ir（Ⅲ）催化苯胺和烯酮还原偶联合成四氢喹啉和高烯丙基苯胺两种产物，同时也能得到中性的1，2-二氢喹啉产物.在此工作的基础上，我们希望能够进一步实现相同反应组分的氧化偶联.为此，我们仔细分析取代的苯胺与烯酮的可能反应路径，发现可能的关键物种G—含有Rh（Ⅲ）的六元杂环中间体有望实现这类氧化过程，当用丙烯醛做底物时，物种G有可能实现β-氢消除得到氧化的二氢喹啉酮和Cp*RhXH，通常Cp*RhXH很容易发生自身的还原消除得到Cp*Rh（I）使反应终止，但是，丙烯醛的存在有可能重新活化Cp*RhXH使得催化循环一直进行下去.另一种情况是中间体G发生质子解然后脱水得到亚胺物种，亚胺很容易被亲核试剂进攻得到中性的氮杂缩醛类产物.当然，外加银盐氧化剂还有可能得到另一种氧化型的喹啉盐.
基于这种思路，我们发展了Rh（Ⅲ）-催化碳氢活化N-取代的苯胺与丙烯醛/烯酮的选择性偶联反应，反应可以化学选择性专一地制备三类不同的杂环化合物.当氮-吡啶基苯胺与丙烯醛反应时，反应类型为氧化过程，经历了转移氢化的过程，其中烯醛为主要的氢受体，得到二氢喹啉酮产物；如果定位基换成嘧啶时，在相似的反应条件下，反应类型为氧化还原中性过程，生成氮杂缩醛醚类产物；氮-吡啶基苯胺和烯酮反应在AgBF₄的氧化作用下同样可以发生氧化反应得到喹啉盐类化合物.至此，我们实现了导向基团对氧化反应和中性反应的控制，氧化剂的种类对反应路径的改变.反应的底物范围广泛，官能团容忍性好，我们期待这类氧化还原多样性的杂环合成方法能促进更多新颖反应的发现.

关键词:

English

Chemo-selective couplings of anilines and acroleins/enones under substrate control and condition control

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 Date: 29 June 2018
Revised Date: 05 July 2018
Fund Project:
This work was supported by the National Nature Science Foundation of China (21525208, 21472186) and the fund for new technology of methanol conversion of Dalian Institute of Chemical Physics (Chinese Academy of Sciences).

Abstract: Rh(Ⅲ)-catalyzed C-H activation of N-protected anilines and chemo-divergent couplings with acroleins/enones have been realized for synthesis of three classes of heterocycles. The oxidative coupling of N-pyridylaniline afforded dihydroquinolones with the acrolein being a major hydrogen acceptor. When the directing group was replaced by pyrimidyl in the same system, redox-neutral coupling occurred to afford hemiaminal ethers. Oxidative annulation of N-pyridylanilines with enones using AgBF₄ oxidant afforded atropisomeric quinolinium salts.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

底物与条件控制苯胺与丙烯醛/烯酮的化学选择性偶联反应

English

Chemo-selective couplings of anilines and acroleins/enones under substrate control and condition control

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

底物与条件控制苯胺与丙烯醛/烯酮的化学选择性偶联反应

English

Chemo-selective couplings of anilines and acroleins/enones under substrate control and condition control

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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