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

doi:10.6023/cjoc202308009

Chinese Journal of Organic Chemistry ›› 2023, Vol. 43 ›› Issue (10): 3608-3613.DOI: 10.6023/cjoc202308009 Previous Articles Next Articles

Special Issue: 有机硅化学专辑-2023

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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Abstract

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

Cite this article

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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Fig. & Tab. 6

Figure 1. Electronic effect controlled regioselective reductive elimination

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

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 (?).

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 (?).

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 (?).

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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