光催化酰基自由基与缺电子1,3-二烯的选择性1,6-加成反应实现羧酸的脱氧烯丙基化

doi:10.1016/S1872-2067(23)64461-4

催化学报 ›› 2023, Vol. 50: 215-221.DOI: 10.1016/S1872-2067(23)64461-4

光催化酰基自由基与缺电子1,3-二烯的选择性1,6-加成反应实现羧酸的脱氧烯丙基化

张丽丽^a, 李雨杭^a, 郭镇宇^a, 李艳涛^a, 李埝^a, 李伟鹏^a^,^*(), 朱成建^a^,^b^,^*(), 谢劲^a^,^*()

^a南京大学化学化工学院, 配位化学国家重点实验室, 江苏省先进有机材料重点实验室, 化学和生物医药创新研究院, 江苏南京 210023
^b郑州大学化学与分子工程学院绿色催化中心, 河南郑州 450001

收稿日期:2023-04-14 接受日期:2023-05-08 出版日期:2023-07-18 发布日期:2023-07-25
通讯作者: *电子信箱: lwp1989@nju.edu.cn (李伟鹏), cjzhu@nju.edu.cn (朱成建), xie@nju.edu.cn (谢劲).
基金资助:
国家重点研发项目(2022YFA1503200);国家重点研发项目(2021YFC2101901);国家自然科学基金(22122103);国家自然科学基金(21971108);国家自然科学基金(21971111);国家自然科学基金(22271144);中央高校基本科研业务费(020514380304);中央高校基本科研业务费(020514380252);中央高校基本科研业务费(020514380272);江苏省研究生科研与实践创新计划项目(KYCX22_0100)

Photoredox deoxygenative allylation of carboxylic acids via selective 1,6-addition of acyl radicals to electron-deficient 1,3-dienes

Lili Zhang^a, Yuhang Li^a, Zhenyu Guo^a, Yantao Li^a, Nian Li^a, Weipeng Li^a^,^*(), Chengjian Zhu^a^,^b^,^*(), Jin Xie^a^,^*()

^aState Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, Jiangsu, China
^bGreen Catalysis Center, College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, Henan, China

Received:2023-04-14 Accepted:2023-05-08 Online:2023-07-18 Published:2023-07-25
Contact: *E-mail: lwp1989@nju.edu.cn (W. Li), cjzhu@nju.edu.cn (C. Zhu), xie@nju.edu.cn (J. Xie).
Supported by:
National Key Research and Development Program of China(2022YFA1503200);National Key Research and Development Program of China(2021YFC2101901);National Natural Science Foundation of China(22122103);National Natural Science Foundation of China(21971108);National Natural Science Foundation of China(21971111);National Natural Science Foundation of China(22271144);Fundamental Research Funds for the Central Universities(020514380304);Fundamental Research Funds for the Central Universities(020514380252);Fundamental Research Funds for the Central Universities(020514380272);Postgraduate Research & Practice Innovation Program of Jiangsu Province(KYCX22_0100)

摘要/Abstract

摘要：

缺电子1,3-二烯类化合物在有机合成和材料科学领域具有重要应用. 由于共轭效应的影响, 该类化合物的化学转化不同于普通烯烃. 一方面, 1,3-二烯有多个反应位点, 可以合成结构多样化的有机化合物, 但另一方面, 多反应位点的存在会使其面临1,4-/1,6-区域选择性和Z/E立体选择性的难题. 由于电子效应通过共轭π体系的传导差异, 使得羰基1,3-二烯的δ位反应活性比β位低, 因此1,6-加成反应较难发生. 虽然过渡金属催化和有机催化方法的开发在一定程度上解决了1,6-加成选择性的问题, 但使用温和的、易得的亲核体实现1,3-二烯的1,6-加成仍是一个难题. 近年来, 可见光驱动的光氧化还原催化提供了温和的自由基生成条件. 一系列自由基前体被应用于不饱和羰基化合物的1,4-加成反应. 然而, 亲核碳自由基在1,6-加成反应中的应用非常少见, 这是因为反应过程中生成的烯丙基自由基中间体容易进一步与二烯反应, 发生聚合竞争反应.

酰基自由基在有机转化中发挥了重要作用, 基于前期本课题组在此方面的工作进展, 本文利用可见光与有机膦的协同作用生成酰基自由基, 通过酰基自由基对羰基1,3-二烯的1,6-共轭加成反应, 实现了芳香羧酸的烯丙基化. 经过对膦试剂、碱和反应溶剂等反应条件的筛选和优化, 以86%的收率得到目标产物. 随后, 在此温和条件下对反应适用性进行考察, 该反应对各种吸电子和给电子的邻、间、对位取代的芳香羧酸都具有很好的兼容性, 各种官能团取代的(杂)芳香羧酸和环烯基甲酸与不同类型的羰基1,3-二烯均能顺利反应, 以高达96%的收率高选择性地获得了一系列E构型的不饱和1,6-二羰基化合物. 对于环酮缺电子二烯, 利用该策略能够高选择性地合成共轭环烯酮. 另外, 将反应规模扩大至5 mmol时, 反应收率几乎不受影响, 成功实现了克级制备. 自由基捕获实验表明酰基自由基参与了该反应. 循环伏安法实验表明三(4-甲氧基苯基)膦能够很容易被失电子的光催化剂氧化, 形成三芳基膦阳离子自由基, 从而诱导羧酸脱氧. Stern-Volmer猝灭实验验证了激发态的光催化剂与羰基1,3-二烯的单电子转移过程, 羰基1,3-二烯被还原为自由基阴离子中间体. 酰基自由基能够迅速与其偶联生成阴离子中间体, 随后经过质子化和异构化得到目标产物. 综上, 本文丰富了可见光催化芳香羧酸的脱氧官能团化反应类型, 并为羰基1,3-二烯的转化提供了新的策略, 为1,6-二羰基化合物的高效合成提供了一种新方法.

关键词: 光氧化还原, 酰基自由基, 1,3-二烯, 1,6-共轭加成, 1,6-二羰基化合物

Abstract:

We report the 1,6-addition of acyl radicals to the electron-deficient 1,3-dienes under visible-light photoredox catalysis. The deoxygenative allylation of the carboxylic acid is achieved under mild conditions, generating the valuable 1,6-dicarbonyl compounds in moderate to good yields (up to 96%). A range of functionalized carboxylic acids are competent coupling partners. This deoxygenative allylation protocol has a high level of regio- and stereo-selectivity as well as good functional group comparability.

Key words: Photoredox catalysis, Acyl radical, 1,3-Dienes, 1,6-Conjugate addition, 1,6-Dicarbonyl compound

张丽丽, 李雨杭, 郭镇宇, 李艳涛, 李埝, 李伟鹏, 朱成建, 谢劲. 光催化酰基自由基与缺电子1,3-二烯的选择性1,6-加成反应实现羧酸的脱氧烯丙基化[J]. 催化学报, 2023, 50: 215-221.

Lili Zhang, Yuhang Li, Zhenyu Guo, Yantao Li, Nian Li, Weipeng Li, Chengjian Zhu, Jin Xie. Photoredox deoxygenative allylation of carboxylic acids via selective 1,6-addition of acyl radicals to electron-deficient 1,3-dienes[J]. Chinese Journal of Catalysis, 2023, 50: 215-221.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64461-4

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图/表 8

Scheme 1. Research progress in functionalization of electron-deficient 1,3-dienes.

Table 1 Optimization of the reaction conditions.

Entry	Additive	Base	Solvent	Yield/%	Conv./%^c
1	Ph₃P	K₂HPO₄	DCM	45^a	48
2	Ph₃P	K₂HPO₄	MeCN	trace	13
3	Ph₃P	K₂HPO₄	DMF	17^a	16
4	Ph₃P	K₂HPO₄	DCM:H₂O (4:1)	53^a	61
5	Ph₂POEt	K₂HPO₄	DCM:H₂O (4:1)	ND	5
6	P(p-Tolyl)₃	K₂HPO₄	DCM:H₂O (4:1)	60^a	71
7	P(p-Anisole)₃	K₂HPO₄	DCM:H₂O (4:1)	78^a (75^b)	84
8	P(p-Anisole)₃	Li₂CO₃	DCM:H₂O (4:1)	71^b	91
9	P(p-Anisole)₃	di-iso-propylamine	DCM:H₂O (4:1)	74^b	82
10	P(p-Anisole)₃	TMP	DCM:H₂O (4:1)	65^b	79
11	P(p-Anisole)₃	di-iso-butylamine	DCM:H₂O (4:1)	83^b	91
12	P(p-Anisole)₃	di-iso-butylamine	DCM:H₂O (9:1)	86^b	93
13^d	P(p-Anisole)₃	di-iso-butylamine	DCM:H₂O (9:1)	39^b	55
14^e	—	di-iso-butylamine	DCM:H₂O (9:1)	ND	0

Scheme 2. Scope of carboxylic acids. E:Z > 95:5 in all cases of 1,6-addition determined by 1H NMR. Reaction conditions: 1 (0.1 mmol), 2a (0.3 mmol), PC-I (2 mol%), P(p-Anisoles)3 (1.2 equiv.), di-iso-butylamine (20 mol%), DCM/H2O (2.0 mL, v/v = 9:1), Ar, rt, 10 W blue LEDs (460 nm), 12 h. a Average yield of three shots.

Scheme 3. Scope of aromatic acids and electron-deficient 1,3-dienes. E:Z > 95:5 in all cases determined by 1H NMR. Reaction conditions: 1 (0.1 mmol), 2 (0.3 mmol), PC-I (2 mol%), P(p-Anisoles)3 (1.2 equiv.), di-iso-butylamine (20 mol%), DCM/H2O (2.0 mL, v/v = 9:1), Ar, rt, 10 W blue LEDs (460 nm), 12 h.

Scheme 4. Gram-scale synthesis of 3aa and control experiments.

Figure 1. The graph of fluorescence quenching of PC-I* by 1a (a), 2a (b) and P(p-Anisole)3 (c), and their Stern-Volmer curves (d).

Figure 2. Cyclic Voltammetry (CV) experiments.

Scheme 5. Proposed mechanism.

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光催化酰基自由基与缺电子1,3-二烯的选择性1,6-加成反应实现羧酸的脱氧烯丙基化

Photoredox deoxygenative allylation of carboxylic acids via selective 1,6-addition of acyl radicals to electron-deficient 1,3-dienes

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