Desaturation via Redox-Neutral Hydrogen Transfer Process: Synthesis of 2-Allyl Anilines, Mechanism and Applications
Yang Zheng,
Ping Dai,
Dafang Gao,
Kemiao Hong,
Luyao Kou,
Shanliang Dong,
Jundie Hu,
Lihua Qiu,
Wenhao Hu,
Xiaoguang Bao,
Xinfang Xu
Affiliations
Yang Zheng
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science Soochow University, Suzhou 215123, China
Ping Dai
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science Soochow University, Suzhou 215123, China
Dafang Gao
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science Soochow University, Suzhou 215123, China
Kemiao Hong
Guangdong Key Laboratory of Chiral Molecule and Drug Discovery, School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou 510006, China
Luyao Kou
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science Soochow University, Suzhou 215123, China
Shanliang Dong
Guangdong Key Laboratory of Chiral Molecule and Drug Discovery, School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou 510006, China
Jundie Hu
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science Soochow University, Suzhou 215123, China; Institute of Materials Science and Devices, Suzhou University of Science and Technology, Suzhou 215003, China
Lihua Qiu
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science Soochow University, Suzhou 215123, China
Wenhao Hu
Guangdong Key Laboratory of Chiral Molecule and Drug Discovery, School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou 510006, China; Corresponding author
Xiaoguang Bao
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science Soochow University, Suzhou 215123, China; Corresponding author
Xinfang Xu
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science Soochow University, Suzhou 215123, China; Guangdong Key Laboratory of Chiral Molecule and Drug Discovery, School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou 510006, China; Corresponding author
Summary: An unprecedented desaturation method via redox-neutral hydrogen transfer process has been disclosed under mild conditions for the selective formation of terminal alkene with alkyl diazo compounds and aza-o-QMs. The control experiments and DFT calculations suggest that the visible light was introduced as a key parameter to enhance the reactivity via a radical process in the formation of closed-shell cyclopropane intermediate, followed by a ring opening and redox-neutral hydrogen transfer process to give the desaturated product. The high regioselectivity in this transformation is enabled by the internal amino species as an ancillary group (AG) in the final olefin formation step. This method provides a missing link in the expeditious preparation of synthetically useful 2-allyl anilines with broad substrate generality. Further applications of these generated products in N-heterocycle construction, including 5- and 6-membered rings with structural diversity, have been tactfully explored, which highlight the potential in methodology development and drug discovery.
