Catalytic Enantioselective Synthesis of Boron-Stereogenic and Axially Chiral BODIPYs via Rhodium(II)-Catalyzed C−H (Hetero) Arylation with Diazonaphthoquinones and Diazoindenines
Yankun Gao
State Key Laboratory for Quality Ensurance and Sustainable Use of Dao-di Herbs, Institute of Medicinal Plant Development, Chinese Academy of Medical Science & Peking Union Medical College, Beijing, 100193 China
These authors contributed equally to this work.
Search for more papers by this authorZizhen Liu
State Key Laboratory for Quality Ensurance and Sustainable Use of Dao-di Herbs, Institute of Medicinal Plant Development, Chinese Academy of Medical Science & Peking Union Medical College, Beijing, 100193 China
These authors contributed equally to this work.
Search for more papers by this authorSichao Tian
State Key Laboratory for Quality Ensurance and Sustainable Use of Dao-di Herbs, Institute of Medicinal Plant Development, Chinese Academy of Medical Science & Peking Union Medical College, Beijing, 100193 China
Search for more papers by this authorYing Min
State Key Laboratory for Quality Ensurance and Sustainable Use of Dao-di Herbs, Institute of Medicinal Plant Development, Chinese Academy of Medical Science & Peking Union Medical College, Beijing, 100193 China
Search for more papers by this authorXiangyu Li
State Key Laboratory for Quality Ensurance and Sustainable Use of Dao-di Herbs, Institute of Medicinal Plant Development, Chinese Academy of Medical Science & Peking Union Medical College, Beijing, 100193 China
Search for more papers by this authorYuxi Chen
State Key Laboratory for Quality Ensurance and Sustainable Use of Dao-di Herbs, Institute of Medicinal Plant Development, Chinese Academy of Medical Science & Peking Union Medical College, Beijing, 100193 China
Search for more papers by this authorCorresponding Author
Prof. Xin Hong
Center of Chemistry for Frontier Technologies, Department of Chemistry, State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou, 310027 China
School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, 453007 China
Search for more papers by this authorCorresponding Author
Prof. Weidong Zhang
State Key Laboratory for Quality Ensurance and Sustainable Use of Dao-di Herbs, Institute of Medicinal Plant Development, Chinese Academy of Medical Science & Peking Union Medical College, Beijing, 100193 China
Search for more papers by this authorCorresponding Author
Prof. Lei Wang
State Key Laboratory for Quality Ensurance and Sustainable Use of Dao-di Herbs, Institute of Medicinal Plant Development, Chinese Academy of Medical Science & Peking Union Medical College, Beijing, 100193 China
Hainan Branch of the Institute of Medicinal Plant Development, Chinese Academy of Medical Sciences & Peking Union Medical College, Haikou, Hainan, 570311 China
Search for more papers by this authorYankun Gao
State Key Laboratory for Quality Ensurance and Sustainable Use of Dao-di Herbs, Institute of Medicinal Plant Development, Chinese Academy of Medical Science & Peking Union Medical College, Beijing, 100193 China
These authors contributed equally to this work.
Search for more papers by this authorZizhen Liu
State Key Laboratory for Quality Ensurance and Sustainable Use of Dao-di Herbs, Institute of Medicinal Plant Development, Chinese Academy of Medical Science & Peking Union Medical College, Beijing, 100193 China
These authors contributed equally to this work.
Search for more papers by this authorSichao Tian
State Key Laboratory for Quality Ensurance and Sustainable Use of Dao-di Herbs, Institute of Medicinal Plant Development, Chinese Academy of Medical Science & Peking Union Medical College, Beijing, 100193 China
Search for more papers by this authorYing Min
State Key Laboratory for Quality Ensurance and Sustainable Use of Dao-di Herbs, Institute of Medicinal Plant Development, Chinese Academy of Medical Science & Peking Union Medical College, Beijing, 100193 China
Search for more papers by this authorXiangyu Li
State Key Laboratory for Quality Ensurance and Sustainable Use of Dao-di Herbs, Institute of Medicinal Plant Development, Chinese Academy of Medical Science & Peking Union Medical College, Beijing, 100193 China
Search for more papers by this authorYuxi Chen
State Key Laboratory for Quality Ensurance and Sustainable Use of Dao-di Herbs, Institute of Medicinal Plant Development, Chinese Academy of Medical Science & Peking Union Medical College, Beijing, 100193 China
Search for more papers by this authorCorresponding Author
Prof. Xin Hong
Center of Chemistry for Frontier Technologies, Department of Chemistry, State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou, 310027 China
School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, 453007 China
Search for more papers by this authorCorresponding Author
Prof. Weidong Zhang
State Key Laboratory for Quality Ensurance and Sustainable Use of Dao-di Herbs, Institute of Medicinal Plant Development, Chinese Academy of Medical Science & Peking Union Medical College, Beijing, 100193 China
Search for more papers by this authorCorresponding Author
Prof. Lei Wang
State Key Laboratory for Quality Ensurance and Sustainable Use of Dao-di Herbs, Institute of Medicinal Plant Development, Chinese Academy of Medical Science & Peking Union Medical College, Beijing, 100193 China
Hainan Branch of the Institute of Medicinal Plant Development, Chinese Academy of Medical Sciences & Peking Union Medical College, Haikou, Hainan, 570311 China
Search for more papers by this authorGraphical Abstract
The rhodium-catalyzed asymmetric reaction between boron dipyrromethenes (BODIPYs) and a variety of naphthodiazoquinones and diazoindenines via C−H (hetero)arylation pathways selectively leads to 2-(hetero)arylated boron-stereogenic and axially chiral BODIPYs in high yields and excellent stereoselectivities. The synthetic value of the procedures is showcased by BODIPY-derived functional molecule construction and scaffold diversification. Bioapplications of tailored BODIPYs indicate their promising properties in multidisciplinary research.
Abstract
The molecular engineering of boron dipyrromethenes (BODIPYs) has garnered widespread attention due to their structural diversity enabling tailored physicochemical properties for optimal applications. However, catalytic enantioselective synthesis of structurally diverse boron-stereogenic BODIPYs through intermolecular desymmetrization and BODIPYs with atroposelectivity remains elusive. Here, we showcase rhodium(II)-catalyzed site-specific C−H (hetero)arylations of prochiral BODIPYs and polysubstituted BODIPYs with diazonaphthoquinonesand diazoindenines, providing efficient pathways for the rapid assembly of versatile (hetero)arylated boron-stereogenic and axially chiral BODIPYs through long-range desymmetrization and axial rotational restriction modes. The synthetic application of the procedures has been emphasized by the efficient synthesis of BODIPY derivatives with various functions. Photophysical properties, bioimaging, and lipid droplet-specific targeting capability of tailored BODIPYs are also demonstrated, indicating their promising applications in biomedical research, medicinal chemistry, and material science.
Conflict of Interests
The authors declare no conflict of interest.
Open Research
Data Availability Statement
The data that support the findings of this study are available in the supplementary material of this article.
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