基于碳二亚胺调控的甲酸原位产生一氧化碳策略的炔烃氢羧化反应: 二氧化碳的间接利用

doi:10.1016/S1872-2067(21)63848-2

催化学报 ›› 2022, Vol. 43 ›› Issue (7): 1642-1651.DOI: 10.1016/S1872-2067(21)63848-2

• 二氧化碳催化转化专栏 • 上一篇下一篇

基于碳二亚胺调控的甲酸原位产生一氧化碳策略的炔烃氢羧化反应: 二氧化碳的间接利用

夏书梅^,^†, 杨志文^,^†, 陈凯宏, 王宁, 何良年()

南开大学化学学院元素有机国家重点实验室, 天津300071

收稿日期:2021-05-09 接受日期:2021-05-25 出版日期:2022-07-18 发布日期:2021-06-09
通讯作者: 何良年
作者简介:第一联系人：
^†共同第一作者.
基金资助:
国家自然科学基金(21975135);国家自然科学基金(22005154)

Efficient hydrocarboxylation of alkynes based on carbodiimide-regulated in situ CO generation from HCOOH: An alternative indirect utilization of CO₂

Shu-Mei Xia^,^†, Zhi-Wen Yang^,^†, Kai-Hong Chen, Ning Wang, Liang-Nian He()

State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China

Received:2021-05-09 Accepted:2021-05-25 Online:2022-07-18 Published:2021-06-09
Contact: Liang-Nian He
About author:First author contact:
^†Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(21975135);National Natural Science Foundation of China(22005154)

摘要/Abstract

摘要：

α,β-不饱和羧酸广泛存在于医药与生物活性分子中, 丙烯酸作为最简单的α,β-不饱和羧酸, 广泛应用于聚合塑料、涂料、橡胶和超强吸水剂的合成, 其工业年需求量已超过上百万吨. 炔烃的氢羧化反应是生产这类化合物直接有效的方法. 然而, 这类反应经常使用CO或CO₂作为C1源, 因此, 反应要在安全条件下进行, 有时不可避免地使用当量甚至过量的对空气敏感的金属有机物种或其他还原剂. 甲酸作为一种廉价易得且安全的羰基源及氢源, 是一种理想的C1资源, 因此甲酸参与的化学转化策略将为高附加值精细化学品的合成提供一个有力平台. 同时, CO₂的催化氢化反应易于制得甲酸, 因此甲酸参与的炔烃氢羧化反应也是一种对二氧化碳的间接性利用方式.

另一方面, 调控甲酸原位分解产生CO的量及其羰基化产物的选择性仍然具有挑战. 过渡金属催化剂往往对CO敏感, 因此设计基于甲酸原位释放CO浓度可调控的催化体系对于炔烃的氢羧化反应具有重要意义. 碳二亚胺是一类重要的亚胺类化合物, 是医学上合成多肽、蛋白质和核苷酸的理想有机脱水试剂. 碳二亚胺作为脱水剂仅在少数有机合成中被报道, 而揭示碳二亚胺自身结构与其反应活性之间的关系对拓展其在有机合成中的应用至关重要.

本文采用碳二亚胺作为脱水剂, 钯作为催化剂, 甲酸作为羰基源及氢源, 实现高效炔烃氢羧化反应, 制得了一系列的E型α,β-不饱和羧酸. 值得注意的是, 除了Pd(II)外, 包括Pd(PPh₃)₄或Pd₂(dba)₃在内的Pd(0)也表现出良好的催化活性, 所有目标产物都有较好的化学选择性、区域选择性及E选择性(100%), 并且该体系具有广泛的官能团兼容性, 对称和非对称芳香单炔、脂肪单炔及芳香二炔烃都成功地得到相应的羧酸产物(50%‒97%). 控制实验、反应动力学研究及同位素标记结果表明, 脱水剂的用量及其结构对甲酸分解起决定性作用, 调控碳二亚胺的种类及浓度, 从而调控原位释放CO的浓度, 是该体系中的关键步骤. 研究结果进一步揭示了碳二亚胺的结构与反应活性之间的关系, 为其在有机合成中的广泛应用铺垫了基石. DFT计算表明, 高浓度的CO会毒化催化剂, 导致反应终止. 本文利用甲酸作为C1源高效实现了炔烃的氢羧化反应, 作为一种CO₂间接利用的新方法, 为CO₂化学转化提供了一种新思路. 另外, 该催化体系实现了可调控原位释放CO浓度, 避免了直接操作高毒性的CO, 为设计可控CO量参与的羰基化及羧化反应提供了安全高效的新途径.

关键词: 碳二亚胺, 氢羧化反应, 甲酸, 二氧化碳间接利用, α,β-不饱和羧酸, 合成方法

Abstract:

The role of carbodiimide as dehydrant in the chemo-, regio- and stereoselective Pd (II/0)-catalyzed hydrocarboxylation of various alkynes with HCOOH releasing CO in situ is reported for the first time to obtain α,β-unsaturated carboxylic acids. Both symmetrical and unsymmetrical monoalkynes show good reactivity. Importantly, 2,2’-(1,4-phenylene)diacrylic acid can also be synthesized in high yield through the dihydrocarboxylation of 1,4-diethynylbenzene. Besides, an excellent result in gram scale experiment and TON up to 900 can be obtained, displaying the efficiency of this protocol. Notably, regulating the types and concentrations of dehydrant can control the CO generation, avoiding directly operating toxic CO and circumventing sensitivity issue to the CO amount. On the basis of the attractive features of formic acid including easy preparation through CO₂ hydrogenation and efficient liberation of CO, this protocol using formic acid as bridging reagent between CO₂ and CO can be perceived as an indirect utilization of CO₂, offering an alternative method for preparing acrylic acid analogues.

Key words: Carbodiimide, Hydrocarboxylation, Formic acid, CO₂ indirect utilization, α,β-Unsaturated carboxylic acids, Synthetic method

夏书梅, 杨志文, 陈凯宏, 王宁, 何良年. 基于碳二亚胺调控的甲酸原位产生一氧化碳策略的炔烃氢羧化反应: 二氧化碳的间接利用[J]. 催化学报, 2022, 43(7): 1642-1651.

Shu-Mei Xia, Zhi-Wen Yang, Kai-Hong Chen, Ning Wang, Liang-Nian He. Efficient hydrocarboxylation of alkynes based on carbodiimide-regulated in situ CO generation from HCOOH: An alternative indirect utilization of CO₂[J]. Chinese Journal of Catalysis, 2022, 43(7): 1642-1651.

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图/表 12

Fig. 1. Transition-metal-catalyzed hydrocarboxylation of alkynes with C1 sources.

Fig. 2. Optimization of the reaction conditions. (a) Effect of 1 mol% different catalysts. (b) Effect of 2 mol% different ligands. (c) Effect of 20 mol% different dehydrants. Template reaction conditions: 1a (1 mmol), Pd(OAc)2 (1 mol%), Xantphos (2 mol%), HCOOH (1.5 mmol), DCC (20 mol%), toluene (2 mL), 80 °C, 12 h, Ar atmosphere. Yields were determined by 1H NMR with triphenylmethane as internal standard. a Ligand (4 mol%). b Ligand (1 mol%). c Pd(OAc)2 (0.2 mol%), Xantphos (0.4 mol%). d Pd(PPh3)4 (0.1 mol%), Xantphos (0.2 mol%).

Fig. 3. The effect of the amount of DCC on the hydrocarboxylation reaction. Reaction conditions: 1a (1 mmol), Pd(OAc)2 (0.2 mol%), Xantphos (0.4 mol%), HCOOH (1.5 mmol), DCC (x mol% relative to 1a), toluene (2 mL), 80 °C, 12 h.

Scheme 1. Scope of symmetric alkynes. Standard conditions: symmetric alkyne 1 (1.0 mmol), Pd(OAc)2 (0.2 mol%), Xantphos (0.4 mol%), HCOOH (1.5 mmol), DCC (20 mol%), toluene (2 mL), 80 °C, 12 h, Ar atmosphere. The yield was determined by 1H NMR with triphenylmethane as internal standard, isolated yields were shown in brackets. a 1a (10.0 mmol), 20 h or 48 h. b Pd(OAc)2 (0.02 mol%), Xantphos (0.04 mol%). c Pd(OAc)2 (0.4 mol%), Xantphos (0.8 mol%).

Scheme 2. Scope of unsymmetric alkynes. The reactions were carried out with internal alkyne (1.0 mmol), Pd(OAc)2 (0.4 mol%), Xantphos (0.8 mol%), HCOOH (1.5 mmol), DCC (20 mol%), toluene (2 mL), 80 °C, 12 h, Ar atmosphere. The yield and the ratio of α and β were determined by 1H NMR with triphenylmethane as internal standard, isolated yield was shown in brackets. a Pd(OAc)2 (1 mol%), Xantphos (2 mol%), 20 h. b α and β configuration couldn’t be distinguished from 1H NMR spectra.

Scheme 3. Scope of terminal alkynes. All reactions were performed in toluene (2 mL) at 80 °C for 20 h in the presence of terminal alkyne (1 mmol), Pd(OAc)2 (1 mol%), Xantphos (2 mol%), HCOOH (1.5 mmol), DCC (20 mol%). The yield and the ratio of α and β were determined by 1H NMR with triphenylmethane as internal standard, isolated yields were shown in brackets. a HCOOH (3 mmol), DCC (40 mol%).

Scheme 4. 13C-Labeling and D-labeling experiments. The yield was determined by 1H NMR with triphenylmethane as internal standard.

Scheme 5. Hydrocarboxylation of 1,2-diphenylethyne with labeled compounds. The yield was determined by 1H NMR with triphenylmethane as internal standard; isolated yields are in brackets.

Table 1 Control experiments: the role of HCOOH.a


Entry	HCOOH/x mmol	DCC/y mol%	CO/z	2a Yield ^b/%
1	0	20	1 atm	—
2	0	20	200 μmol	—
3	1.5	—	200 μmol	64
4	1.5	20	—	97

Fig. 4. The relationship between the release amount of CO from dehydrant and the reaction outcome. Reaction conditions A: diphenylacetylene 1a (1 mmol), Pd(OAc)2 (0.2 mol%), Xantphos (0.4 mol%), dehydrant (20 mol%), HCOOH (1.5 mmol), toluene (2 mL), 80 °C, 12 h, yield determined by 1H NMR. Reaction conditions B: Pd(OAc)2 (0.2 mol%), Xantphos (0.4 mol%), HCOOH (1.5 mmol), dehydrant (20 mol%), toluene (2 mL), 80 °C, 12 h, Ar atmosphere, the release amount of CO was determined by GC with CH4 as internal standard. a No dehydrant. b No dehydrant, CO (200 μmol).

Scheme 6. DFT calculations on catalyst poisoning for (Xantphos)Pd(CO).

Fig. 5. Proposed mechanism for the Pd-catalyzed regioselective hydrocarboxylation using HCOOH.

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基于碳二亚胺调控的甲酸原位产生一氧化碳策略的炔烃氢羧化反应: 二氧化碳的间接利用

Efficient hydrocarboxylation of alkynes based on carbodiimide-regulated in situ CO generation from HCOOH: An alternative indirect utilization of CO₂

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基于碳二亚胺调控的甲酸原位产生一氧化碳策略的炔烃氢羧化反应: 二氧化碳的间接利用

Efficient hydrocarboxylation of alkynes based on carbodiimide-regulated in situ CO generation from HCOOH: An alternative indirect utilization of CO2

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Efficient hydrocarboxylation of alkynes based on carbodiimide-regulated in situ CO generation from HCOOH: An alternative indirect utilization of CO₂