One-Pot Preparation of Bridged Tricyclic and Fused Tetracyclic Scaffolds via Rhodium(III)-Catalyzed Asymmetric Borylative Cyclization
Summary: Bridged and fused polycyclic structures are found in a huge number of natural products. Significant progress has been made on their syntheses; however, facile and practical strategies to afford polycycles with tunable substituents and functional groups remain rare. Here, we report a practic...
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| Format: | Article |
| Language: | English |
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Elsevier
2020-10-01
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| Series: | Cell Reports Physical Science |
| Online Access: | http://www.sciencedirect.com/science/article/pii/S266638642030237X |
| _version_ | 1818426854991724544 |
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| author | Qing-Hua Li Dingding Gao Cheng-Yu He Qi Liao Yun-Xuan Tan Yu-Hui Wang Rui Ding Guo-Qiang Lin Ping Tian |
| author_facet | Qing-Hua Li Dingding Gao Cheng-Yu He Qi Liao Yun-Xuan Tan Yu-Hui Wang Rui Ding Guo-Qiang Lin Ping Tian |
| author_sort | Qing-Hua Li |
| collection | DOAJ |
| description | Summary: Bridged and fused polycyclic structures are found in a huge number of natural products. Significant progress has been made on their syntheses; however, facile and practical strategies to afford polycycles with tunable substituents and functional groups remain rare. Here, we report a practical rhodium(III)-catalyzed asymmetric borylative cyclization of cyclohexadienone-containing 1,6-enynes, affording highly enantioenriched cis-bicyclic frameworks with great functional group compatibility, and further extend it to construct bridged tricyclic and fused tetracyclic skeletons in one-pot protocols. The combination of borylative cyclization with a subsequent oxidation/aldol reaction sequence goes through an epimerization of the stereocenter adjacent to the acetyl group, yielding various tricyclic compounds. In addition, borylative cyclization is combined with a Suzuki-Miyaura coupling/Michael addition sequence, leading to diverse tetracyclic compounds. Starting from simple starting materials, both one-pot transformations yield complex products bearing several consecutive stereocenters with excellent enantioselectivities. Furthermore, an unnatural steroid-like compound is also readily prepared, demonstrating the potential of this methodology. |
| first_indexed | 2024-12-14T14:36:27Z |
| format | Article |
| id | doaj.art-8968a8f4a05b4d878bc7f978718e5cc6 |
| institution | Directory Open Access Journal |
| issn | 2666-3864 |
| language | English |
| last_indexed | 2024-12-14T14:36:27Z |
| publishDate | 2020-10-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Cell Reports Physical Science |
| spelling | doaj.art-8968a8f4a05b4d878bc7f978718e5cc62022-12-21T22:57:36ZengElsevierCell Reports Physical Science2666-38642020-10-01110100222One-Pot Preparation of Bridged Tricyclic and Fused Tetracyclic Scaffolds via Rhodium(III)-Catalyzed Asymmetric Borylative CyclizationQing-Hua Li0Dingding Gao1Cheng-Yu He2Qi Liao3Yun-Xuan Tan4Yu-Hui Wang5Rui Ding6Guo-Qiang Lin7Ping Tian8The Research Center of Chiral Drugs, Innovation Research Institute of Traditional Chinese Medicine, Shanghai University of Traditional Chinese Medicine, Shanghai 201203, ChinaThe Research Center of Chiral Drugs, Innovation Research Institute of Traditional Chinese Medicine, Shanghai University of Traditional Chinese Medicine, Shanghai 201203, ChinaCAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, ChinaThe Research Center of Chiral Drugs, Innovation Research Institute of Traditional Chinese Medicine, Shanghai University of Traditional Chinese Medicine, Shanghai 201203, ChinaCAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, ChinaThe Research Center of Chiral Drugs, Innovation Research Institute of Traditional Chinese Medicine, Shanghai University of Traditional Chinese Medicine, Shanghai 201203, China; Corresponding authorThe Research Center of Chiral Drugs, Innovation Research Institute of Traditional Chinese Medicine, Shanghai University of Traditional Chinese Medicine, Shanghai 201203, China; Corresponding authorThe Research Center of Chiral Drugs, Innovation Research Institute of Traditional Chinese Medicine, Shanghai University of Traditional Chinese Medicine, Shanghai 201203, China; CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, ChinaThe Research Center of Chiral Drugs, Innovation Research Institute of Traditional Chinese Medicine, Shanghai University of Traditional Chinese Medicine, Shanghai 201203, China; CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, China; Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Shanghai Jiao Tong University, Shanghai 200240, China; Corresponding authorSummary: Bridged and fused polycyclic structures are found in a huge number of natural products. Significant progress has been made on their syntheses; however, facile and practical strategies to afford polycycles with tunable substituents and functional groups remain rare. Here, we report a practical rhodium(III)-catalyzed asymmetric borylative cyclization of cyclohexadienone-containing 1,6-enynes, affording highly enantioenriched cis-bicyclic frameworks with great functional group compatibility, and further extend it to construct bridged tricyclic and fused tetracyclic skeletons in one-pot protocols. The combination of borylative cyclization with a subsequent oxidation/aldol reaction sequence goes through an epimerization of the stereocenter adjacent to the acetyl group, yielding various tricyclic compounds. In addition, borylative cyclization is combined with a Suzuki-Miyaura coupling/Michael addition sequence, leading to diverse tetracyclic compounds. Starting from simple starting materials, both one-pot transformations yield complex products bearing several consecutive stereocenters with excellent enantioselectivities. Furthermore, an unnatural steroid-like compound is also readily prepared, demonstrating the potential of this methodology.http://www.sciencedirect.com/science/article/pii/S266638642030237X |
| spellingShingle | Qing-Hua Li Dingding Gao Cheng-Yu He Qi Liao Yun-Xuan Tan Yu-Hui Wang Rui Ding Guo-Qiang Lin Ping Tian One-Pot Preparation of Bridged Tricyclic and Fused Tetracyclic Scaffolds via Rhodium(III)-Catalyzed Asymmetric Borylative Cyclization Cell Reports Physical Science |
| title | One-Pot Preparation of Bridged Tricyclic and Fused Tetracyclic Scaffolds via Rhodium(III)-Catalyzed Asymmetric Borylative Cyclization |
| title_full | One-Pot Preparation of Bridged Tricyclic and Fused Tetracyclic Scaffolds via Rhodium(III)-Catalyzed Asymmetric Borylative Cyclization |
| title_fullStr | One-Pot Preparation of Bridged Tricyclic and Fused Tetracyclic Scaffolds via Rhodium(III)-Catalyzed Asymmetric Borylative Cyclization |
| title_full_unstemmed | One-Pot Preparation of Bridged Tricyclic and Fused Tetracyclic Scaffolds via Rhodium(III)-Catalyzed Asymmetric Borylative Cyclization |
| title_short | One-Pot Preparation of Bridged Tricyclic and Fused Tetracyclic Scaffolds via Rhodium(III)-Catalyzed Asymmetric Borylative Cyclization |
| title_sort | one pot preparation of bridged tricyclic and fused tetracyclic scaffolds via rhodium iii catalyzed asymmetric borylative cyclization |
| url | http://www.sciencedirect.com/science/article/pii/S266638642030237X |
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