区域选择性地电化学氧化自由基参与的邻位-(4 + 2)/原位-(3 + 2)环化

doi:10.1016/S1872-2067(23)64510-3

催化学报 ›› 2023, Vol. 52: 144-153.DOI: 10.1016/S1872-2067(23)64510-3

区域选择性地电化学氧化自由基参与的邻位-(4 + 2)/原位-(3 + 2)环化

关志朋^,¹, 杨东锋^,¹, 刘钊, 朱书祥, 仲星星, 王华敏, 李向伟, 戚孝天^*(), 易红^*(), 雷爱文^*()

武汉大学化学与分子科学学院, 高等研究院, 湖北武汉430072

收稿日期:2023-07-14 接受日期:2023-08-21 出版日期:2023-09-18 发布日期:2023-09-25
通讯作者: *电子信箱: hong.yi@whu.edu.cn (易红),qi7xiaotian@whu.edu.cn (戚孝天),aiwenlei@whu.edu.cn (雷爱文).
作者简介:¹共同第一作者.
基金资助:
中国博士后科学基金(2021M702516);国家重点研发计划(2022YFA15001500);国家重点研发计划(2021YFA1500100);国家自然科学基金(22031008);武汉市科学基金(2020010601012192);广东省基础与应用基础研究基金(2023A1515012260);中央高校基本科研业务费(2042022rc0030)

Regioselective electrochemical oxidative radical ortho-(4 + 2)/ipso-(3 + 2) cyclization

Zhipeng Guan^,¹, Dongfeng Yang^,¹, Zhao Liu, Shuxiang Zhu, Xingxing Zhong, Huamin Wang, Xiangwei Li, Xiaotian Qi^*(), Hong Yi^*(), Aiwen Lei^*()

The Institute for Advanced Studies (IAS), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, Hubei, China

Received:2023-07-14 Accepted:2023-08-21 Online:2023-09-18 Published:2023-09-25
Contact: *E-mail: hong.yi@whu.edu.cn (H. Yi),qi7xiaotian@whu.edu.cn (X. Qi),aiwenlei@whu.edu.cn (A. Lei).
About author:¹Contributed equally to this work.
Supported by:
China Postdoctoral Science Foundation(2021M702516);National Key R&D Program of China(2022YFA15001500);National Key R&D Program of China(2021YFA1500100);National Natural Science Foundation of China(22031008);Science Foundation of Wuhan(2020010601012192);Guangdong Basic and Applied Basic Research Foundation(2023A1515012260);Fundamental Research Funds for the Central Universities(2042022rc0030)

摘要/Abstract

摘要：

碳环化合物, 特别是五元环和六元环骨架, 广泛存在于天然产物和生物活性分子中. Diels-Alder环加成反应是构建这些功能型分子的有效方法, 但其底物适用范围有限, 且反应条件 (如热、微波和过渡金属的使用)苛刻, 限制了该方法的应用. 自由基物种含有不成对的价电子, 表现出高活性, 在温和的反应条件下提供了新的反应途径. 因此, 自由基介导的反应为复杂环状分子的合成提供了一个新平台. 然而, 如何实现选择性自由基环化仍然是一个挑战. 鲍德温规则为自由基物种与烯烃炔烃的加成提供了指导, 研究人员设计并开发了一系列反应模式构建所需的五元和六元环分子. 但是, 自由基物种, 特别是烷基和烯基与芳基之间选择性的邻位原位环化仍然不明确.

本文利用苄基丙二酸酯为自由基源, 烯烃和炔烃分别为自由基受体, 分别获得烷基和烯基自由基中间体, 并探究烷基自由基和烯基自由基与芳基之间的选择性环化. 利用二茂铁介导的电化学氧化策略, 进行了烷基/烯基自由基与芳基的选择性环化实验. 结果表明, 烷基自由基与芳环发生选择性邻位-(4 + 2)环化, 烯基自由基与芳环发生选择性原位-(3 + 2)环化. 理论研究结果表明, 促进烯烃优先邻位加成的主要原因是有利的相互作用能; 炔烃优先原位加成区域选择性由形变能量控制. 重要的是, 该策略被认为是鲍德温自由基环化规则的重要补充. 此外, 对二茂铁介导的电化学氧化苄基丙二酸酯的C‒H键官能团化进行了深入的机理研究. 自由基捕获实验证明了苄基丙二酸酯碳自由基的存在. 循环伏安测试结果表明, 苄基丙二酸酯碳负离子与二茂铁之间存在电子转移. 阳极电势实验证明了二茂铁在该自由基反应中的作用; 同位素实验揭示了螺环化合物氧的来源.

本文合成了一系列四氢萘和螺环衍生物, 表现出较好的底物适用范围和官能团耐受性, 且该方法避免了化学氧化剂/碱/贵金属的使用、底物的预官能团化以及底物的过氧化. 综上, 本文为实现自由基的区域选择性环化提供了参考.

关键词: 区域选择性, 自由基, 邻位-(4 + 2)/原位-(3 + 2)环化, 电化学氧化, 碳环化合物

Abstract:

Achieving regioselectivity in radical cyclization reactions is of central importance, yet extremely challenging. Although Baldwin’s rules provided guidance on the addition of radical species with alkenes/alkynes, the ortho-/ipso-selectivity of the cyclic reaction between radical species (especially alkyl and alkenyl radical) and aryl groups is still ambiguous. Herein, we develop an electrochemically enabled regioselective ortho-(4 + 2)/ipso-(3 + 2) cyclization of alkyl/alkenyl radicals with aryl groups, which provides a series of tetrahydronaphthalene and spirocarbocycle derivatives, exhibiting a broad substrate scope and functional group tolerance. Alkyl/alkenyl radicals are generated by Cp₂Fe-mediated electrochemical oxidative radical addition of benzylic malonates with alkenes and alkynes. The method avoids the use of chemical oxidant/base/noble metal, the pre-functionalization of substrates, and the over-oxidation of compounds. Theoretical studies reveal that the dominant factor promoting the alkene-preferred ortho-addition is the favorable interaction energy; the alkyne-preferred ipso-addition regioselectivity is controlled by the distortion energy. Notably, this strategy is regarded as an important supplement to Baldwin’s rules for radical cyclization.

Key words: Regioselectivity, Radical, Ortho-(4 + 2)/ipso-(3 + 2) cyclization, Electrochemical oxidation, Carbocyclic compound

关志朋, 杨东锋, 刘钊, 朱书祥, 仲星星, 王华敏, 李向伟, 戚孝天, 易红, 雷爱文. 区域选择性地电化学氧化自由基参与的邻位-(4 + 2)/原位-(3 + 2)环化[J]. 催化学报, 2023, 52: 144-153.

Zhipeng Guan, Dongfeng Yang, Zhao Liu, Shuxiang Zhu, Xingxing Zhong, Huamin Wang, Xiangwei Li, Xiaotian Qi, Hong Yi, Aiwen Lei. Regioselective electrochemical oxidative radical ortho-(4 + 2)/ipso-(3 + 2) cyclization[J]. Chinese Journal of Catalysis, 2023, 52: 144-153.

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图/表 6

Scheme 1. Instruction of radical cyclization reaction and our design and work.

Scheme 2. Studies of electrochemical ortho-(4 + 2) cyclization between benzylic malonates and alkenes. Reaction conditions: benzylic substrates (0.5 mmol), alkenes (0.2 mmol), Cp2Fe (0.02 mmol), nBu4NBF4 (1.0 mmol), MeOH (4 mL), DME (2 mL), carbon felt anode, Pt cathode, undivided cell, constant current = 5 mA, 3.75 h, rt, N2. Isolated yield.

Scheme 3. Studies of ipso-(3 + 2) spirocyclization benzylic malonates and alkenes. Reaction conditions: benzylic substrates (0.3 mmol), alkynes (0.2 mmol), Cp2Fe (0.02 mmol), nBu4NBF4 (1.0 mmol), H2O (100 μL), MeOH (6 mL), carbon felt anode, Pt cathode, undivided cell, constant current = 5 mA, 3.25 h, 50 °C, N2. Isolated yield.

Scheme 4. Scope of substrates of the ipso-(3 + 2) spirocyclization. Reaction Conditions: benzylic substrates (0.3 mmol), alkynes (0.2 mmol), Cp2Fe (0.02 mmol), nBu4NBF4 (1.0 mmol), H2O (100 μL), MeOH (6 mL), carbon felt anode, Pt cathode, undivided cell, constant current = 5 mA, 3.25 h, 50 °C, N2. Isolated yield.

Scheme 5. Derivatization of product and mechanistic studies.

Scheme 6. Proposed reaction mechanism.

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区域选择性地电化学氧化自由基参与的邻位-(4 + 2)/原位-(3 + 2)环化

Regioselective electrochemical oxidative radical ortho-(4 + 2)/ipso-(3 + 2) cyclization

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