Brønsted Acid Catalyzed Dearomatization by Intramolecular Hydroalkoxylation/Claisen Rearrangement: Diastereo- and Enantioselective Synthesis of Spirolactams
Peng-Fei Chen
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
These authors contributed equally to this work.
Search for more papers by this authorBo Zhou
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
These authors contributed equally to this work.
Search for more papers by this authorPeng Wu
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
Search for more papers by this authorProf. Dr. Binju Wang
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Long-Wu Ye
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
State Key Laboratory of Organometallic Chemistry, Shanghai, Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032 China
State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin, 300071 China
Search for more papers by this authorPeng-Fei Chen
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
These authors contributed equally to this work.
Search for more papers by this authorBo Zhou
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
These authors contributed equally to this work.
Search for more papers by this authorPeng Wu
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
Search for more papers by this authorProf. Dr. Binju Wang
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Long-Wu Ye
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
State Key Laboratory of Organometallic Chemistry, Shanghai, Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032 China
State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin, 300071 China
Search for more papers by this authorDedicated to the 100th anniversary of Xiamen University
Graphical Abstract
A Brønsted acid catalyzed intramolecular hydroalkoxylation/Claisen rearrangement is disclosed that involves an unexpected dearomatization of nonactivated arenes and heteroaromatic compounds and allows the practical and atom-economic synthesis of various valuable spirolactams. Moreover, the asymmetric version of this tandem cyclization is also achieved via kinetic resolution by chiral phosphoric acid catalysis.
Abstract
Described herein is a novel Brønsted acid catalyzed intramolecular hydroalkoxylation/Claisen rearrangement, allowing the practical and atom-economic synthesis of a range of valuable spirolactams from readily available ynamides in generally good to excellent yields with excellent diastereoselectivities and broad substrate scope. Importantly, an unexpected dearomatization of nonactivated arenes and heteroaromatic compounds is involved in this tandem sequence. Moreover, an asymmetric version of this tandem cyclization was also achieved by efficient kinetic resolution by chiral phosphoric acid catalysis. In addition, the [3,3]-rearrangement is shown to be kinetically preferred over the related [1,3]-rearrangement by theoretical calculations.
Conflict of interest
The authors declare no conflict of interest.
Supporting Information
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