取代基电性效应对碳硅还原消除区域选择性调控的理论研究

doi:10.6023/cjoc202308009

有机化学 ›› 2023, Vol. 43 ›› Issue (10): 3608-3613.DOI: 10.6023/cjoc202308009 上一篇下一篇

所属专题：有机硅化学专辑-2023

研究论文

取代基电性效应对碳硅还原消除区域选择性调控的理论研究

彭菊^a, 何晓倩^a, 廖黎丽^a^,^*(), 白若鹏^a^,^*(), 蓝宇^a^,^b^,^*()

a 重庆大学化学化工学院理论与计算化学重庆市重点实验室重庆 401331
b 郑州大学化学学院绿色催化中心郑州 450001

收稿日期:2023-08-11 修回日期:2023-08-29 发布日期:2023-08-31
作者简介:
† 共同第一作者
基金资助:
国家自然科学基金(22003006); 国家自然科学基金(22201027); 国家自然科学基金(22271034); 中国博士后科学基金(2021M700578)

Theoretical Study of How Electronic Effect of Substituent Affects Regioselectivity of C—Si Reductive Elimination

Ju Peng^a, Xiaoqian He^a, Li-Li Liao^a(), Ruopeng Bai^a(), Yu Lan^a^,^b()

a School of Chemistry and Chemical Engineering, Chongqing Key Laboratory of Theoretical and Computational Chemistry, Chongqing University, Chongqing 401331
b Green Catalysis Center, College of Chemistry, Zhengzhou University, Zhengzhou 450001

Received:2023-08-11 Revised:2023-08-29 Published:2023-08-31
Contact: *E-mail: liaoll@cqu.edu.cn; ruopeng@cqu.edu.cn; lanyu@cqu.edu.cn
About author:
† These authors contributed equally to this work
Supported by:
National Natural Science Foundation of China(22003006); National Natural Science Foundation of China(22201027); National Natural Science Foundation of China(22271034); China Postdoctoral Science Foundation(2021M700578)

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摘要/Abstract

有机反应区域选择性的调控是有机化学的重要研究内容之一, 而电性效应则是其重要调控因素. 运用密度泛函理论计算, 以钯催化2-碘联苯化合物与硅杂环丁烷的环化反应为模板, 研究了取代基电性效应在还原消除过程中对区域选择性的影响, 并给出了该反应的详细反应机理. 计算结果表明, 该反应经历了Pd—I键氧化加成、协同金属去质子、Pd—Si键氧化加成、还原消除过程得到硅杂八元环产物, 且C—Si键还原消除是反应的速率决定步骤. 对Pd(IV)还原消除过渡态中电子效应的研究证明, 当使用不对称2-碘联苯作为反应底物时, 芳环电子密度是区域选择性的主要控制因素, 电子密度更高的基团更容易发生还原消除, 与该基元反应电子流向一致.

关键词: 电性效应, 区域选择性, 还原消除, 密度泛函理论

Regioselectivity adjustment is one of the key research fields in organic chemistry, and electronic effect is the key factor for adjustment. In this work, density functional theory (DFT) calculation was carried out to investigate how electronic effect of substituent affects regioselectivity in the reductive elimination step. Palladium-catalyzed annulation of silacyclo- butanes and 2-iodobiarenes was selected as model reaction, and detailed reaction mechanism is illustrated. The results shows that the reaction undergoes Pd—I bond oxidative addition, concerted metalation deprotonation (CMD), Pd—Si bond oxidative addition, and reductive elimination process to synthesize eight-membered silacycles, and C—Si bond reductive elimination is the rate determining step. Study of electronic effect in Pd(IV) reductive elimination transition state shows that when asymmetrically substituted 2-iodobyphenyl is used as substrate, electron density of aromatic ring is the main factor to control regioselectivity. Groups with higher electron density have higher priority for reductive elimination, and this is in accordance with electron flow in this elementary reaction.

Key words: electronic effect, regioselectivity, reductive elimination, density functional theory

引用此文

彭菊, 何晓倩, 廖黎丽, 白若鹏, 蓝宇. 取代基电性效应对碳硅还原消除区域选择性调控的理论研究[J]. 有机化学, 2023, 43(10): 3608-3613.

Ju Peng, Xiaoqian He, Li-Li Liao, Ruopeng Bai, Yu Lan. Theoretical Study of How Electronic Effect of Substituent Affects Regioselectivity of C—Si Reductive Elimination[J]. Chinese Journal of Organic Chemistry, 2023, 43(10): 3608-3613.

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图/表 6

图1. 电性调控的区域选择性还原消除

Figure 1. Electronic effect controlled regioselective reductive elimination

图2. (a) Pd催化2-碘联苯和硅杂环丁烷的环化反应; (b)可能的反应机理

Figure 2. (a) Palladium-catalyzed annulation of silacyclobutanes and 2?iodobiarenes; (b) proposed catalytic cycle

图3. Pd(0)与2-碘联苯氧化加成生成Pd(II)物种的势能面

Figure 3. Free energy profiles of oxidative addition for Pd(0)-species and 2-iodobiphenyl generates Pd(II) complex Calculations were performed using Gaussian 16 at the M06/def2-TZVP/SMD(DMF)//B3LYP-D3/def2-SVP/SMD(DMF) level of theory and bond lengths are shown in angstroms (?).

图4. 五元环Pd(II)中间体参与的两种路径的势能面

Figure 4. Free energy profiles of five-membered palladacycle intermediate for path A and path B Calculations were performed using Gaussian 16 at the M06/def2-TZVP/SMD(DMF)//B3LYP-D3/def2-SVP/ SMD(DMF) level of theory and bond lengths are shown in angstroms (?).

图5. Pd(0)与硅杂环丁烷氧化加成生成Pd(II)物种的势能面

Figure 5. Free energy profiles of oxidative addition for Pd(0)-species and silacyclobutanes generates Pd(II) complex Calculations were performed using Gaussian 16 at the M06/def2-TZVP/SMD(DMF)//B3LYP-D3/def2-SVP/SMD(DMF) level of theory and bond lengths are shown in angstroms (?).

图6. 还原消除过渡态的区域选择性研究

Figure 6. Study on the regioselectivities of the reductive elimination transition states Calculations were performed using Gaussian 16 at the M06/def2-TZVP/SMD(DMF)//B3LYP-D3/def2-SVP/ SMD(DMF) level of theory and values are shown in kcal/mol.

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取代基电性效应对碳硅还原消除区域选择性调控的理论研究

Theoretical Study of How Electronic Effect of Substituent Affects Regioselectivity of C—Si Reductive Elimination

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