Desymmetrization of Cyclic 1,3-Diketones under N-Heterocyclic Carbene Organocatalysis: Access to Organofluorines with Multiple Stereogenic Centers
Symmetric 1,3-diketones with fluorine or fluorinated substituents on the prochiral carbon remain to be established. Herein, we have developed a novel prochiral fluorinated oxindanyl 1,3-diketone and successfully applied these substrates in carbene-catalyzed asymmetric desymmetrization. Accordingly,...
| Main Authors: | , , , , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
American Association for the Advancement of Science (AAAS)
2021-01-01
|
| Series: | Research |
| Online Access: | http://dx.doi.org/10.34133/2021/9867915 |
| _version_ | 1827333559368548352 |
|---|---|
| author | Guanjie Wang Min Zhang Yezhi Guan Ye Zhang Xianfang Hong Chenlong Wei Pengcheng Zheng Donghui Wei Zhenqian Fu Yonggui Robin Chi Wei Huang |
| author_facet | Guanjie Wang Min Zhang Yezhi Guan Ye Zhang Xianfang Hong Chenlong Wei Pengcheng Zheng Donghui Wei Zhenqian Fu Yonggui Robin Chi Wei Huang |
| author_sort | Guanjie Wang |
| collection | DOAJ |
| description | Symmetric 1,3-diketones with fluorine or fluorinated substituents on the prochiral carbon remain to be established. Herein, we have developed a novel prochiral fluorinated oxindanyl 1,3-diketone and successfully applied these substrates in carbene-catalyzed asymmetric desymmetrization. Accordingly, a versatile strategy for asymmetric generation of organofluorines with fluorine or fluorinated methyl groups has been developed. Multiple stereogenic centers were selectively constructed with satisfactory outcomes. Structurally diverse enantioenriched organofluorines were generated with excellent results in terms of yields, diastereoselectivities, and enantioselectivities. Notably, exchanging fluorinated methyl groups to fluorine for this prochiral 1,3-diketones leads to switchable stereoselectivity. Mechanistic aspects and origin of stereoselectivity were studied by DFT calculations. Notably, some of the prepared organofluorines demonstrated competitive antibacterial activities. |
| first_indexed | 2024-03-07T17:29:11Z |
| format | Article |
| id | doaj.art-6b06d3bc4c0e4b0eb4a1a4b9b7a02331 |
| institution | Directory Open Access Journal |
| issn | 2639-5274 |
| language | English |
| last_indexed | 2024-03-07T17:29:11Z |
| publishDate | 2021-01-01 |
| publisher | American Association for the Advancement of Science (AAAS) |
| record_format | Article |
| series | Research |
| spelling | doaj.art-6b06d3bc4c0e4b0eb4a1a4b9b7a023312024-03-02T18:34:39ZengAmerican Association for the Advancement of Science (AAAS)Research2639-52742021-01-01202110.34133/2021/9867915Desymmetrization of Cyclic 1,3-Diketones under N-Heterocyclic Carbene Organocatalysis: Access to Organofluorines with Multiple Stereogenic CentersGuanjie Wang0Min Zhang1Yezhi Guan2Ye Zhang3Xianfang Hong4Chenlong Wei5Pengcheng Zheng6Donghui Wei7Zhenqian Fu8Yonggui Robin Chi9Wei Huang10Key Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced Materials (IAM) Nanjing Tech University (NanjingTech), 30 South Puzhu Road, Nanjing 211816, ChinaCollege of Chemistry and Green Catalysis Center, Zhengzhou University, Zhengzhou, Henan 450001, ChinaSchool of Chemistry and Molecular Engineering, Nanjing Tech University (NanjingTech), 30 South Puzhu Road, Nanjing 211816, ChinaKey Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced Materials (IAM) Nanjing Tech University (NanjingTech), 30 South Puzhu Road, Nanjing 211816, ChinaKey Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced Materials (IAM) Nanjing Tech University (NanjingTech), 30 South Puzhu Road, Nanjing 211816, ChinaKey Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced Materials (IAM) Nanjing Tech University (NanjingTech), 30 South Puzhu Road, Nanjing 211816, ChinaLaboratory Breeding Base of Green Pesticide and Agricultural Bioengineering, Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education, Guizhou University, Huaxi District, Guiyang 550025, ChinaCollege of Chemistry and Green Catalysis Center, Zhengzhou University, Zhengzhou, Henan 450001, ChinaKey Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced Materials (IAM) Nanjing Tech University (NanjingTech), 30 South Puzhu Road, Nanjing 211816, ChinaLaboratory Breeding Base of Green Pesticide and Agricultural Bioengineering, Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education, Guizhou University, Huaxi District, Guiyang 550025, China; Division of Chemistry & Biological Chemistry, School of Physical & Mathematical Sciences, Nanyang Technological University, Singapore, SingaporeKey Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced Materials (IAM) Nanjing Tech University (NanjingTech), 30 South Puzhu Road, Nanjing 211816, China; Frontiers Science Center for Flexible Electronics (FSCFE) & Shaanxi Institute of Flexible Electronics (SIFE), Northwestern Polytechnical University (NPU), 127 West Youyi Road, Xi’an 710072, ChinaSymmetric 1,3-diketones with fluorine or fluorinated substituents on the prochiral carbon remain to be established. Herein, we have developed a novel prochiral fluorinated oxindanyl 1,3-diketone and successfully applied these substrates in carbene-catalyzed asymmetric desymmetrization. Accordingly, a versatile strategy for asymmetric generation of organofluorines with fluorine or fluorinated methyl groups has been developed. Multiple stereogenic centers were selectively constructed with satisfactory outcomes. Structurally diverse enantioenriched organofluorines were generated with excellent results in terms of yields, diastereoselectivities, and enantioselectivities. Notably, exchanging fluorinated methyl groups to fluorine for this prochiral 1,3-diketones leads to switchable stereoselectivity. Mechanistic aspects and origin of stereoselectivity were studied by DFT calculations. Notably, some of the prepared organofluorines demonstrated competitive antibacterial activities.http://dx.doi.org/10.34133/2021/9867915 |
| spellingShingle | Guanjie Wang Min Zhang Yezhi Guan Ye Zhang Xianfang Hong Chenlong Wei Pengcheng Zheng Donghui Wei Zhenqian Fu Yonggui Robin Chi Wei Huang Desymmetrization of Cyclic 1,3-Diketones under N-Heterocyclic Carbene Organocatalysis: Access to Organofluorines with Multiple Stereogenic Centers Research |
| title | Desymmetrization of Cyclic 1,3-Diketones under N-Heterocyclic Carbene Organocatalysis: Access to Organofluorines with Multiple Stereogenic Centers |
| title_full | Desymmetrization of Cyclic 1,3-Diketones under N-Heterocyclic Carbene Organocatalysis: Access to Organofluorines with Multiple Stereogenic Centers |
| title_fullStr | Desymmetrization of Cyclic 1,3-Diketones under N-Heterocyclic Carbene Organocatalysis: Access to Organofluorines with Multiple Stereogenic Centers |
| title_full_unstemmed | Desymmetrization of Cyclic 1,3-Diketones under N-Heterocyclic Carbene Organocatalysis: Access to Organofluorines with Multiple Stereogenic Centers |
| title_short | Desymmetrization of Cyclic 1,3-Diketones under N-Heterocyclic Carbene Organocatalysis: Access to Organofluorines with Multiple Stereogenic Centers |
| title_sort | desymmetrization of cyclic 1 3 diketones under n heterocyclic carbene organocatalysis access to organofluorines with multiple stereogenic centers |
| url | http://dx.doi.org/10.34133/2021/9867915 |
| work_keys_str_mv | AT guanjiewang desymmetrizationofcyclic13diketonesundernheterocycliccarbeneorganocatalysisaccesstoorganofluorineswithmultiplestereogeniccenters AT minzhang desymmetrizationofcyclic13diketonesundernheterocycliccarbeneorganocatalysisaccesstoorganofluorineswithmultiplestereogeniccenters AT yezhiguan desymmetrizationofcyclic13diketonesundernheterocycliccarbeneorganocatalysisaccesstoorganofluorineswithmultiplestereogeniccenters AT yezhang desymmetrizationofcyclic13diketonesundernheterocycliccarbeneorganocatalysisaccesstoorganofluorineswithmultiplestereogeniccenters AT xianfanghong desymmetrizationofcyclic13diketonesundernheterocycliccarbeneorganocatalysisaccesstoorganofluorineswithmultiplestereogeniccenters AT chenlongwei desymmetrizationofcyclic13diketonesundernheterocycliccarbeneorganocatalysisaccesstoorganofluorineswithmultiplestereogeniccenters AT pengchengzheng desymmetrizationofcyclic13diketonesundernheterocycliccarbeneorganocatalysisaccesstoorganofluorineswithmultiplestereogeniccenters AT donghuiwei desymmetrizationofcyclic13diketonesundernheterocycliccarbeneorganocatalysisaccesstoorganofluorineswithmultiplestereogeniccenters AT zhenqianfu desymmetrizationofcyclic13diketonesundernheterocycliccarbeneorganocatalysisaccesstoorganofluorineswithmultiplestereogeniccenters AT yongguirobinchi desymmetrizationofcyclic13diketonesundernheterocycliccarbeneorganocatalysisaccesstoorganofluorineswithmultiplestereogeniccenters AT weihuang desymmetrizationofcyclic13diketonesundernheterocycliccarbeneorganocatalysisaccesstoorganofluorineswithmultiplestereogeniccenters |