无金属条件下以酰基膦酸酯为烷基自由基受体的分子间酰化反应

doi:10.6023/cjoc202207044

有机化学 ›› 2022, Vol. 42 ›› Issue (12): 4332-4339.DOI: 10.6023/cjoc202207044 上一篇下一篇

所属专题：自由基化学专辑

研究论文

无金属条件下以酰基膦酸酯为烷基自由基受体的分子间酰化反应

方晶^a, 闵庆强^a, 秦海涛^a^,^*(), 刘峰^a^,^b^,^*()

a 苏州大学药学院江苏省神经精神疾病重点实验室和药物化学系苏州 215123
b 中国科学院上海有机化学研究所有机氟化学重点实验室上海200032

收稿日期:2022-07-30 修回日期:2022-08-26 发布日期:2022-09-08
通讯作者: 秦海涛, 刘峰
基金资助:
国家自然科学基金(22171200)

Intermolecular Acylation with Acylphosphonates as Alkyl Radical Receptor under Metal-Free Conditions

Jing Fang^a, Qingqiang Min^a, Haitao Qin^a(), Feng Liu^a^,^b()

a Jiangsu Key Laboratory of Neuropsychiatric Diseases and Department of Medicinal Chemistry, College of Pharmaceutical Sciences, Soochow University, Suzhou 215123
b Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Received:2022-07-30 Revised:2022-08-26 Published:2022-09-08
Contact: Haitao Qin, Feng Liu
Supported by:
National Natural Science Foundation of China(22171200)

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摘要/Abstract

羰基作为有机化学中的中心官能团之一, 可以通过多种途径合成, 但是利用酰基膦酸酯为酰基供体进行的分子间的自由基反应还鲜有报道. 分别研究了在热化学和光化学条件下, 酰基膦酸酯作为自由基受体分别和烷基醛、汉斯酯及烷烃三种自由基供体之间的酰化反应. 以烷基醛和烷烃作为自由基前体时, 在微波加热以及氧化剂存在的条件下, 分子间的酰化反应可以顺利进行; 而以汉斯酯作为自由基前体时, 在紫外光照射及室温条件下, 即可以顺利发生分子间的酰化反应.

关键词: 酰基膦酸酯, 自由基受体, 分子间酰化反应

As one of the central functional groups in organic chemistry, carbonyl skeleton can be achieved by many ways, but the intermolecular radical reaction using acyl phosphonate as acyl donor is rarely reported. The acylation reaction between acyl phosphonate as a free radical acceptor and three free radical donors, alkyl aldehyde, Hans ester and alkane, was studied under thermochemical and photochemical conditions, respectively. When alkyl aldehydes and alkanes were used as radical precursors, the intermolecular acylation reaction could proceed smoothly under the conditions of microwave heating and the presence of oxidants. When Hantzsch esters were used as the radical precursors, the intermolecular acylation reaction could take place smoothly under UV irradiation at room temperature.

Key words: acylphosphonate, radical acceptor, intermolecular acylation reaction

引用此文

方晶, 闵庆强, 秦海涛, 刘峰. 无金属条件下以酰基膦酸酯为烷基自由基受体的分子间酰化反应[J]. 有机化学, 2022, 42(12): 4332-4339.

Jing Fang, Qingqiang Min, Haitao Qin, Feng Liu. Intermolecular Acylation with Acylphosphonates as Alkyl Radical Receptor under Metal-Free Conditions[J]. Chinese Journal of Organic Chemistry, 2022, 42(12): 4332-4339.

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图/表 3

图式1. 以酰基膦酸酯为底物合成羰基化合物

Scheme 1. Synthesis of carbonyl compound with acylphosphonates

表1. 酰基膦酸酯为底物的适用性拓展a,b

Table 1. Substrae scope with acylphosphonates

图式2. 可能的反应机理

Scheme 2. Proposed mechanism

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无金属条件下以酰基膦酸酯为烷基自由基受体的分子间酰化反应

Intermolecular Acylation with Acylphosphonates as Alkyl Radical Receptor under Metal-Free Conditions

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