Switchable organocatalytic enantioselective sulfenocyclization of cyclohexadienes enabling chemodivergent access to chiral bicyclo[m.n.1] ring systems
Abstract The precise control over regio- and stereoselectivity from the same substrate represents a significant challenge in organic chemistry. Herein, a switchable organocatalytic enantioselective carbosulfenylation/sulfenolactonization of cyclohexa-1,4-dienes to access the chiral bicyclo[m.n.1] ri...
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Nature Portfolio
2025-05-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-59918-5 |
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| author | Bing-Qian Zhang Lei Chen Wen-Ying Xiao Yidong Liu Yin-Long Li Jun Deng |
| author_facet | Bing-Qian Zhang Lei Chen Wen-Ying Xiao Yidong Liu Yin-Long Li Jun Deng |
| author_sort | Bing-Qian Zhang |
| collection | DOAJ |
| description | Abstract The precise control over regio- and stereoselectivity from the same substrate represents a significant challenge in organic chemistry. Herein, a switchable organocatalytic enantioselective carbosulfenylation/sulfenolactonization of cyclohexa-1,4-dienes to access the chiral bicyclo[m.n.1] ring systems, which are the critical core skeleton of many important natural products and biologically active compounds, is achieved. By simply tuning the substituent of the sulfenylating agent, a series of synthetically challenging chiral bridged bicyclo[3.3.1]nonanes and 2-oxabicyclo[3.2.1]octanes bearing three consecutive stereocenters are obtained with good yields and excellent enantioselectivities (up to 94% yield and 97% ee). Furthermore, the initial investigation of the bicyclic derivative as a chiral ligand in metal catalysis is also conducted. Our findings offer a version of switchable divergent asymmetric synthesis in which different products can be controllably generated from an identical set of substrates by simply adjusting reaction parameters. |
| format | Article |
| id | doaj-art-c356c242bb714f1889b23b31fb2809f5 |
| institution | DOAJ |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-05-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-c356c242bb714f1889b23b31fb2809f52025-08-20T03:08:43ZengNature PortfolioNature Communications2041-17232025-05-0116111010.1038/s41467-025-59918-5Switchable organocatalytic enantioselective sulfenocyclization of cyclohexadienes enabling chemodivergent access to chiral bicyclo[m.n.1] ring systemsBing-Qian Zhang0Lei Chen1Wen-Ying Xiao2Yidong Liu3Yin-Long Li4Jun Deng5Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, School of Pharmaceutical Sciences, Chongqing UniversityChongqing Key Laboratory of Natural Product Synthesis and Drug Research, School of Pharmaceutical Sciences, Chongqing UniversityChongqing Key Laboratory of Natural Product Synthesis and Drug Research, School of Pharmaceutical Sciences, Chongqing UniversityChongqing Key Laboratory of Natural Product Synthesis and Drug Research, School of Pharmaceutical Sciences, Chongqing UniversityDepartment of Radiology and Imaging Sciences, Emory University, 1364 Clifton RdChongqing Key Laboratory of Natural Product Synthesis and Drug Research, School of Pharmaceutical Sciences, Chongqing UniversityAbstract The precise control over regio- and stereoselectivity from the same substrate represents a significant challenge in organic chemistry. Herein, a switchable organocatalytic enantioselective carbosulfenylation/sulfenolactonization of cyclohexa-1,4-dienes to access the chiral bicyclo[m.n.1] ring systems, which are the critical core skeleton of many important natural products and biologically active compounds, is achieved. By simply tuning the substituent of the sulfenylating agent, a series of synthetically challenging chiral bridged bicyclo[3.3.1]nonanes and 2-oxabicyclo[3.2.1]octanes bearing three consecutive stereocenters are obtained with good yields and excellent enantioselectivities (up to 94% yield and 97% ee). Furthermore, the initial investigation of the bicyclic derivative as a chiral ligand in metal catalysis is also conducted. Our findings offer a version of switchable divergent asymmetric synthesis in which different products can be controllably generated from an identical set of substrates by simply adjusting reaction parameters.https://doi.org/10.1038/s41467-025-59918-5 |
| spellingShingle | Bing-Qian Zhang Lei Chen Wen-Ying Xiao Yidong Liu Yin-Long Li Jun Deng Switchable organocatalytic enantioselective sulfenocyclization of cyclohexadienes enabling chemodivergent access to chiral bicyclo[m.n.1] ring systems Nature Communications |
| title | Switchable organocatalytic enantioselective sulfenocyclization of cyclohexadienes enabling chemodivergent access to chiral bicyclo[m.n.1] ring systems |
| title_full | Switchable organocatalytic enantioselective sulfenocyclization of cyclohexadienes enabling chemodivergent access to chiral bicyclo[m.n.1] ring systems |
| title_fullStr | Switchable organocatalytic enantioselective sulfenocyclization of cyclohexadienes enabling chemodivergent access to chiral bicyclo[m.n.1] ring systems |
| title_full_unstemmed | Switchable organocatalytic enantioselective sulfenocyclization of cyclohexadienes enabling chemodivergent access to chiral bicyclo[m.n.1] ring systems |
| title_short | Switchable organocatalytic enantioselective sulfenocyclization of cyclohexadienes enabling chemodivergent access to chiral bicyclo[m.n.1] ring systems |
| title_sort | switchable organocatalytic enantioselective sulfenocyclization of cyclohexadienes enabling chemodivergent access to chiral bicyclo m n 1 ring systems |
| url | https://doi.org/10.1038/s41467-025-59918-5 |
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