银催化的硅烷氧基炔和羰基化合物的[2+2]环加成机理:硅正离子迁移主导的过程

doi:10.6023/cjoc202106038

有机化学 ›› 2021, Vol. 41 ›› Issue (11): 4327-4337.DOI: 10.6023/cjoc202106038 上一篇下一篇

研究论文

银催化的硅烷氧基炔和羰基化合物的[2+2]环加成机理:硅正离子迁移主导的过程

王恒定^a^,^b, 江凌^a^,^b, 梁鸿雁^c, 樊红军^a^,^b^,^*()

a 中国科学院大连化学物理研究所分子反应动力学国家重点实验室辽宁大连 116023
b 中国科学院大学北京 100864
c 西宁特钢技术中心西宁 810005

收稿日期:2021-06-22 修回日期:2021-08-04 发布日期:2021-08-24
通讯作者: 樊红军
基金资助:
国家重点研发计划(2016YFB0600301); 国家自然科学基金(92061114); 国家自然科学基金(21873096); 中科院战略先导计划(XDB17010200)

Mechanism of Silver-Catalyzed [2+2] Cycloaddition between Siloxy-Alkynes and Carbonyl Compound: A Silylium Ion Migration Approach

Hengding Wang^a^,^b, Ling Jiang^a^,^b, Hongyan Liang^c, Hongjun Fan^a^,^b()

a State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023
b University of Chinese Academy of Sciences, Beijing 100864
c Technical Center, Xining Special Steel Co Ltd., Xining 810005

Received:2021-06-22 Revised:2021-08-04 Published:2021-08-24
Contact: Hongjun Fan
Supported by:
National Key Research and Development Program of China(2016YFB0600301); National Natural Science Foundation of China(92061114); National Natural Science Foundation of China(21873096); Strategic Priority Research Program of Chinese Academy of Sciences(XDB17010200)

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摘要/Abstract

银离子可以高效地催化硅烷氧基炔与α,β-不饱和羰基化合物之间的[2+2]环加成反应, 在银离子催化下硅烷氧基炔可以与甲醛的羰基发生[2+2]环加成后开环生成不饱和酯. 利用密度泛函理论(DFT)计算发现, 在这两个反应中银离子与硅烷氧基炔之间相互作用, 将硅烷氧基炔激活成为硅正离子和银烯酮, 硅正离子进一步催化羰基化合物(α,β-不饱和羰基化合物或者醛)和银烯酮之间的[2+2]环加成反应.

关键词: 硅正离子, [2+2]环加成, 银烯酮, 醛的烯化, 硅烷氧基炔

Mechanism of silver-catalyzed [2+2] cycloaddition between siloxy-alkynes and α,β-unsaturated carbonyl compound remains controversial. Based on density functional theory (DFT) calculation, it is revealed that Ag⁺ activate siloxy-alkyne into silver-ketene and silylium ion (TIPS⁺) in this reaction. TIPS⁺ then promote [2+2] cycloaddition between α,β-unsaturated carbonyl compound and silver-ketene to form cyclobutane-intermediate, which undergos TIPS⁺ migration and transforms into final product. The mechanism of Ag⁺ catalyzed olefination of aldehydes using siloxy-alkynes was also investigated, the results showed that TIPS⁺ migration also took place in this reaction. In the two reactions studied, Ag⁺ interacts with π-bond of siloxy-alkynes and triggers TIPS⁺ migration, which offers alternative solution to silylium-catalyzed reaction. As similarity of ynolates, silver-ketenes are more stable, which can undergo 1,4-nucleophilic addition with α,β- unsaturated compound. For [2+2] cycloaddition, catalytic variant is rather limited, this work provides a different perspective to obtain four-membered ring products or its ring-open derivates.

Key words: silylium ion, [2+2] cycloaddition, silver-ketene, olefination of aldehyde, siloxy-alkyne

引用此文

王恒定, 江凌, 梁鸿雁, 樊红军. 银催化的硅烷氧基炔和羰基化合物的[2+2]环加成机理:硅正离子迁移主导的过程[J]. 有机化学, 2021, 41(11): 4327-4337.

Hengding Wang, Ling Jiang, Hongyan Liang, Hongjun Fan. Mechanism of Silver-Catalyzed [2+2] Cycloaddition between Siloxy-Alkynes and Carbonyl Compound: A Silylium Ion Migration Approach[J]. Chinese Journal of Organic Chemistry, 2021, 41(11): 4327-4337.

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图/表 9

Scheme 1. Reactions between siloxy-alkynes and carbonyl compound in the presence of π-acid

Scheme 2. Our proposed π-acid and silylium ion exchange mechanism

Figure 1. Free energy profile for TIPSOTf catalyzed [2+2] cycloaddition between siloxy-alkyne 1a and 3-buten-2-one (2a) (a) Free energy profile; (b) Optimized geometries. Gibbs free energies and electronic energy are in kcal/mol. Hydrogen atom was omitted for clarity. Triisopropylsilyl (TIPS) is simplified into big ball except desilication process and versa.

Figure 2. Free energy profile for C—C coupling (a) Free energy profile; (b) Optimized geometries. Gibbs free energies are in kcal/mol. Hydrogen atom was omitted and coordinated ligand was white cloaked for clarity. Triisopropylsilyl (TIPS) is simplified into big ball except desilication process.

Figure 3. Free energy profile for formation final product 3a (a) Free energy profile; (b) Optimized geometries. Gibbs free energies are in kcal/mol. Hydrogen atom was omitted and coordinated ligand was white cloaked for clarity. Triisopropylsilyl (TIPS) is simplified into big ball except desilication process and versa.

Scheme 3. Diastereoselective experiment and deuterium label experiment reported by Kozmin and coworkers

Figure 4. NCI plot of transition states E-A-ts2 and Z-A-ts2 Blue represents strong attraction; green represents van der Waals interaction; red represents strong repulsion or steric effect.

Figure 5. Free energy profiles of olefination of aldehyde using siloxy-alkynes Gibbs free energies are in kcal/mol. Hydrogen atom was omitted and coordinated ligand was white cloaked for clarity. Triisopropylsilyl (TIPS) is simplified into big ball. (a) Free energy profile; (b) Optimized geometries

Scheme 4. Comparation of Ag+ stabilized ynolate anion and Li+ stabilized ynolate anion

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银催化的硅烷氧基炔和羰基化合物的[2+2]环加成机理:硅正离子迁移主导的过程

Mechanism of Silver-Catalyzed [2+2] Cycloaddition between Siloxy-Alkynes and Carbonyl Compound: A Silylium Ion Migration Approach

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