Difunctionalization of Unactivated Alkenes through SCF3 Radical-triggered Distal Functional Group Migration

doi:10.6023/A18080313

Acta Chimica Sinica ›› 2018, Vol. 76 ›› Issue (12): 951-955.DOI: 10.6023/A18080313 Previous Articles Next Articles

Special Issue: 有机氟化学

Communication

通过远端碳氮双键迁移实现非活化烯烃的三氟甲硫基化反应

陈栋^a, 吉梅山^a, 姚英明^a, 朱晨^a,b

a. 苏州大学材料与化学化工学部苏州 215123;
b. 中国科学院上海有机化学研究所天然产物有机合成重点实验室上海 200032

投稿日期:2018-08-02 发布日期:2018-08-27
通讯作者: 姚英明,E-mail:yaoym@suda.edu.cn;朱晨,E-mail:chzhu@suda.edu.cn E-mail:yaoym@suda.edu.cn;chzhu@suda.edu.cn
基金资助:
项目受国家自然科学基金（No.21722205）资助.

Difunctionalization of Unactivated Alkenes through SCF₃ Radical-triggered Distal Functional Group Migration

Chen Dong^a, Ji Meishan^a, Yao Yingming^a, Zhu Chen^a,b

a. College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123;
b. Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Received:2018-08-02 Published:2018-08-27
Contact: 10.6023/A18080313 E-mail:yaoym@suda.edu.cn;chzhu@suda.edu.cn
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21722205).

1. Difunctionalization of Unactivated Alkenes through SCF₃ Radical-triggered Distal Functional Group Migration.PDF(8397KB)

Abstract

Radical-mediated C-SCF₃ bond formation via the addition of SCF₃ radical to alkenes has become an efficient strategy for the construction of alkyl trifluoromethylthioethers. However, the scope of alkenes is largely limited to activated alkenes in which the presence of adjacent carbonyl or aryl group is required to stabilize the alkyl radical intermediates by p-π conjugation. A few cases involving trifluoromethylthiolation of unactivated olefins have been reported, but in these reactions only a single functional group is incorporated to alkenes. The radical difunctionalization of unactivated olefins remains challenging and has received less attention. Recently, we established a new protocol to realize the radical difunctionalization of alkenes through intramolecularly distal functional group migration. This tactic provides a useful and elegant tool for the elusive functionalization of unactivated olefins. A portfolio of groups such as cyano, heteroaryl, imino, aldehyde, and alkynyl can be readily migrated in the transformation. Herein, we disclose an efficient and practical approach for the trifluoromethylthiolation of unactivated olefins based on the intramolecular migration of heteroaryl and imino groups. The migration is triggered by the addition of SCF₃ radical, which is generated from the mixture of AgSCF₃ and K₂S₂O₈at room temperature, to alkenes. The reaction demonstrates a high functional group compatibility and broad substrate scope. A variety of nitrogen-containing five- and six-membered heteroaryl as well as imino groups are readily migrated, affording the synthetically valuable alkyl trifluoromethylthioether compounds in good yields. The typical procedure is as follows: a mixture of tertiary alcohol (0.2 mmol), AgSCF₃(0.3 mmol), and K₂S₂O₈(0.6 mmol) is loaded in a flame-dried reaction vial which is subjected to evacuation/flushing with nitrogen three times. Dry DMF (2.0 mL) is added to the mixture via syringe, and the mixture is then stirred at room temperature until the starting material is consumed which is determined by TLC. The mixture is extracted with ethyl acetate (10 mL×3). The combined organic extracts are washed with brine, dried over Na₂SO₄, filtered, concentrated, and purified by flash column chromatography on silica gel (eluent: petroleum ether/ethyl acetate) to give the desired product.

Key words: alkene difunctionalization, trifluoromethylthiolation, migration reaction, radical reaction, heteroaryl

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Chen Dong, Ji Meishan, Yao Yingming, Zhu Chen. Difunctionalization of Unactivated Alkenes through SCF₃ Radical-triggered Distal Functional Group Migration[J]. Acta Chimica Sinica, 2018, 76(12): 951-955.

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通过远端碳氮双键迁移实现非活化烯烃的三氟甲硫基化反应

Difunctionalization of Unactivated Alkenes through SCF₃ Radical-triggered Distal Functional Group Migration

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