亚胺配体协同氮杂环卡宾钯配合物催化碳碳偶联反应的作用机制

doi:10.6023/cjoc202206033

摘要/Abstract

在氮杂环卡宾-钯(NHC-Pd)配合物催化的碳-碳偶联反应中, 配体结构对催化反应起到关键作用. 为了实现更好的催化效果, 不仅要对NHC配体进行结构优化, 还需要第二配体的协同作用. 然而, 由于第二配体配位能力大大弱于NHC配体, 其在催化反应中的协同作用往往被忽视. 合成出了3种由相同结构NHC配体以及不同结构亚胺配体组成的NHC-Pd配合物来催化Suzuki-Miyaura交叉偶联反应. 实验结果表明, 在相同的反应条件下, 3种亚胺配体协同的NHC-Pd配合物表现出了明显不同的催化效果. 进一步采用理论计算来深入研究亚胺配体协同的NHC-Pd配合物在催化反应中的作用机制. 通过完整催化循环过程的计算, 发现虽然亚胺配体并没有参与到催化循环过程中, 但亚胺配体与氯苯会形成竞争配位, 它们与NHC-Pd(0)的配位能力差异直接导致实际参与催化循环的有效活性中心的浓度的差异, 计算表明大位阻缺电子的亚胺配体更有利于反应的进行. 通过研究, 更好地阐明了亚胺配体在催化碳-碳偶联反应中的作用机制, 并为NHC-Pd配合物的结构调控提供了新策略.

关键词: 氮杂环卡宾配体, 亚胺配体, Suzuki-Miyaura交叉偶联反应, 反应机理, 密度泛函理论(DFT)计算

Structure of ligands would play a crucial role in carbon-carbon coupling reactions catalyzed by N-heterocyclic carbene palladium (NHC-Pd) complexes. Not only the modification of NHC ligands but also the synergistic action of the second ligands were required to achieve better catalytic performance. However, the synergistic effect of the second ligands was often overlooked because of their considerably weaker coordination ability. Three NHC-Pd complexes composed of the same structural NHC ligand and different structural imine ligands were utilized to catalyze the Suzuki-Miyaura cross-coupling reaction. The results showed that the three imine-ligand-assisted NHC-Pd complexes exhibited significantly different catalytic effects under the same reaction conditions. Further theoretical calculations were applied to investigate the catalytic reaction mechanism of these imine-ligand-assisted NHC-Pd complexes in depth. By calculations of the complete catalytic cycle process, it was found that although imine ligands were not involved in the catalytic cycle process, competitive coordination between imine ligands and chlorobenzene should be metioned. The difference in their coordination ability with NHC-Pd(0) directly lead to the difference in the concentration of effective active centers actually involved in the catalytic cycle. The large site-blocking and electron-deficient imine-ligand-assisted NHC-Pd complexes were more favorable for the reaction. The study elucidated the mechanism of imine ligands in catalytic carbon-carbon coupling reactions and provided new strategies for the structural modulation of NHC-Pd complexes.

Key words: N-heterocyclic carbene ligand, imine ligand, Suzuki-Miyaura cross coupling reaction, reaction mechanism, density function theory (DFT) calculation

引用此文

刘婷婷, 胡宇才, 沈安. 亚胺配体协同氮杂环卡宾钯配合物催化碳碳偶联反应的作用机制[J]. 有机化学, 2023, 43(2): 622-628.

Tingting Liu, Yucai Hu, An Shen. Mechanism of Carbon-Carbon Coupling Reactions Catalyzed by Imine-Ligand-Assisted N-Heterocyclic Carbene Palladium Complexes[J]. Chinese Journal of Organic Chemistry, 2023, 43(2): 622-628.

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图/表 9

图式1. 交叉偶联反应催化循环机理

Scheme 1. Catalytic cycle mechanism of cross-coupling reaction

图1. 用于交叉偶联反应的典型NHC-Pd配合物

Figure 1. Typical NHC-Pd complexes for cross-coupling reactions

图2. 亚胺-NHC-Pd配合物和X射线单晶衍射结构

Figure 2. Imine-ligand-assisted NHC-Pd complexes and their X-ray structures

Entry	23	NHC-Pd
1	A B C	64 90 97
2	A B C	89 96 96
3	A B C	93 96 >99
4	A B C	95 >99 >99
5	A B C	25 71 88

表1. 不同NHC-Pd配合物催化Suzuki偶联反应结果a

Table 1. Results of different NHC-Pd complexes for Suzuki coupling reaction

图3. 异丙醇溶剂中NHC-Pd A配合物活化过程的能量示意图

Figure 3. Energetic profile for the activation process of NHC-Pd A complex in isopropanol solvent

图4. 异丙醇溶剂中NHC-Pd A配合物在不同氧化加成路径下的能量示意图

Figure 4. Energetic profile of the different pathways for the oxidative addition process of NHC-Pd A complex in isopropanol solvent

图5. 异丙醇溶剂中NHC-Pd A配合物转金属化及还原消除过程的能量示意图及过渡态能量计算

Figure 5. Energetic profile for the transmetallation and reductive elimination process of NHC-Pd A complex in isopropanol solvent

Intermediate/ transition state	NHC-Pd A		NHC-Pd B		NHC-Pd C
Intermediate/ transition state	GAS	SMD	GAS	SMD	GAS	SMD
I1	-4.2	-0.1	-3.7	0.6	-5.6	-0.6
TS1	21.5	20.0	20.6	20.8	20.9	21.0
ΔG^≠(TS1)	25.7	20.1	24.3	20.2	26.5	21.6
I2	0.5	3.1	0.0	3.4	0.7	4.5
I3	-11.8	-12.9	-11.3	-12.5	-10.3	-11.2
TS2	3.6	5.2	3.2	4.8	3.7	6.2
ΔG^≠(TS2)	15.3	18.1	14.6	17.3	14.0	17.4
I4	-25.5	-25.5	-23.5	-22.1	-18.0	-13.8
I5a	-11.5	-13.5	-11.2	-13.8	-11.7	-13.9
I5a-I4	-	12	-	8.3	-	-0.1
I6a	-23.0	-23.4	-22.7	-23.7	-23.2	-23.8
TS3a	-9.6	-6.4	-9.4	-6.7	-9.8	-6.8
ΔG^≠(TS3a)	13.4	17.0	13.4	17.0	13.4	17.0
I7	-14.6	-22.0	-14.3	-22.3	-14.8	-22.5

表2. 不同NHC-Pd配合物的能量计算(kcal/mol)a

Table 2. Computation of different NHC-Pd complexes (kcal/ mol)

图6. 中间体I4~I6的结构参数

Figure 6. Structural parameters of intermediate I4~I6

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