Rational Design of Axially Chiral Styrene-Based Organocatalysts and Their Application in Catalytic Asymmetric (2+4) Cyclizations
Si-Jia Liu
School of Chemistry and Materials Science, Key Laboratory of Green Synthetic Chemistry for Functional Materials of Jiangsu Province, Jiangsu Normal University, Xuzhou, 221116 China
Search for more papers by this authorZhi-Han Chen
School of Chemistry and Materials Science, Key Laboratory of Green Synthetic Chemistry for Functional Materials of Jiangsu Province, Jiangsu Normal University, Xuzhou, 221116 China
Search for more papers by this authorJia-Yi Chen
Department of Chemistry, Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Shantou, 515063 China
Search for more papers by this authorCorresponding Author
Dr. Shao-Fei Ni
Department of Chemistry, Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Shantou, 515063 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Yu-Chen Zhang
School of Chemistry and Materials Science, Key Laboratory of Green Synthetic Chemistry for Functional Materials of Jiangsu Province, Jiangsu Normal University, Xuzhou, 221116 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Feng Shi
School of Chemistry and Materials Science, Key Laboratory of Green Synthetic Chemistry for Functional Materials of Jiangsu Province, Jiangsu Normal University, Xuzhou, 221116 China
Search for more papers by this authorSi-Jia Liu
School of Chemistry and Materials Science, Key Laboratory of Green Synthetic Chemistry for Functional Materials of Jiangsu Province, Jiangsu Normal University, Xuzhou, 221116 China
Search for more papers by this authorZhi-Han Chen
School of Chemistry and Materials Science, Key Laboratory of Green Synthetic Chemistry for Functional Materials of Jiangsu Province, Jiangsu Normal University, Xuzhou, 221116 China
Search for more papers by this authorJia-Yi Chen
Department of Chemistry, Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Shantou, 515063 China
Search for more papers by this authorCorresponding Author
Dr. Shao-Fei Ni
Department of Chemistry, Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Shantou, 515063 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Yu-Chen Zhang
School of Chemistry and Materials Science, Key Laboratory of Green Synthetic Chemistry for Functional Materials of Jiangsu Province, Jiangsu Normal University, Xuzhou, 221116 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Feng Shi
School of Chemistry and Materials Science, Key Laboratory of Green Synthetic Chemistry for Functional Materials of Jiangsu Province, Jiangsu Normal University, Xuzhou, 221116 China
Search for more papers by this authorDedicated to those who are committed to advocating diversity in chemistry
Abstract
A new class of axially chiral styrene-based thiourea tertiary amine catalysts, which have unique characteristics such as an efficient synthetic route, multiple chiral elements, and multiple activating groups, has been rationally designed. These new chiral catalysts have proven to be efficient organocatalysts, enabling the chemo-, diastereo-, and enantioselective (2+4) cyclization of 2-benzothiazolimines with homophthalic anhydrides in good yields (up to 96 %) with excellent stereoselectivities (all >95:5 dr, up to 98 % ee). More importantly, theoretical calculations elucidated the important role of an axially chiral styrene moiety in controlling both the reactivity and enantioselectivity. This work not only represents the first design of styrene-based chiral thiourea tertiary amine catalysts and the first catalytic asymmetric (2+4) cyclization of 2-benzothiazolimines, but also gives an in-depth understanding of axially chiral styrene-based organocatalysts.
Conflict of interest
The authors declare no conflict of interest.
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