无金属条件下芳基酮与二甲亚砜的α-C(sp3)—H亚甲基化反应合成γ-酮亚砜
收稿日期: 2023-04-08
修回日期: 2023-06-25
网络出版日期: 2023-07-13
基金资助
国家自然科学基金(21602035); 广东省科学技术厅(2016A020221038); 广东教育厅(2020ZDZX2054); 广东省自然科学基金(2016A030307030); 广东省自然科学基金(2017A030307006)
Metal-Free α-C(sp3)—H Methylenation of Aryl Ketones to Form γ-Keto Sulfoxides with Dimethyl Sulfoxide
Received date: 2023-04-08
Revised date: 2023-06-25
Online published: 2023-07-13
Supported by
National Natural Science Foundation of China(21602035); Foundation of Department of Science and Technology of Guangdong Province(2016A020221038); Department of Education of Guangdong Province(2020ZDZX2054); Natural Science Foundation of Guangdong Province(2016A030307030); Natural Science Foundation of Guangdong Province(2017A030307006)
芳基酮通过C(sp3)—H键官能化与二甲亚砜发生直接的α-C(sp3)—H亚甲基化反应生成γ-酮亚砜, 该方法适用于各种芳基酮. 此外, 二甲基亚砜(DMSO)在反应中不仅用作溶剂, 而且用作含硫单元. 这种转化的实际价值在于γ-酮亚砜的高效和稳健的一锅合成法, 并在初步实验的基础上, 提出了一种可能的反应机理.
关键词： 芳基酮; C(sp3)—H亚甲基化; 无金属; γ-酮亚砜; 区域选择性
肖朵朵 , 张建涛 , 周鹏 , 刘卫兵 . 无金属条件下芳基酮与二甲亚砜的α-C(sp3)—H亚甲基化反应合成γ-酮亚砜[J]. 有机化学, 2023 , 43(11) : 3900 -3906 . DOI: 10.6023/cjoc202304011
A direct α-C(sp3)—H methylenation of aryl ketones to form γ-keto sulfoxides via C(sp3)—H functionalization with dimethyl sulfoxide has been developed. This method is applicable to a wide range of aryl ketones. Moreover, dimethyl sulfoxide (DMSO) in this reaction is used not only as solvent but also as a sulfur-containing unit. The practical value of this transformation highlights the efficient and robust one-pot synthesis of γ-keto sulfoxides. Based on the preliminary experiments, a plausible reaction mechanism is proposed.
Key words： aryl ketone; C(sp3)—H methylenation; metal-free; γ-keto sulfoxides; regioselectivity
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