Nucleophile-Controlled Regiodivergent Domino Reactions of Enetriones with γ-Bromocrotonates: Access to 1,3-Dienic Esters and Tetrasubstituted Pyrans
Herein, we developed an efficient nucleophile-controlled regiodivergent domino reaction between enetriones and γ-bromocrotonates. This method allowed for the rapid synthesis of a range of 1,3-dienic esters and tetrasubstituted pyrans under metal-free conditions. In the presence of pyridine, a S<sub>N</sub>2 substitution/Michael addition/elimination sequence formed 1,3-dienic esters in satisfactory yields with high <i>E</i>-stereoselectivities. Alternatively, a S<sub>N</sub>2 substitution/Michael addition/cyclization/cyclopropanation/cyclopropane ring-opening process forged tetrasubstituted pyrans in good yields with the help of Et<sub>3</sub>N. It is interesting to note that the site-selective reactions of γ-bromocrotonates at the α- or γ-position were readily realized by modulating pyridine and Et<sub>3</sub>N. Furthermore, the simple pyridine and Et<sub>3</sub>N act as both nucleophiles in S<sub>N</sub>2 substitution reactions and Lewis bases in deprotonation processes.
Authors
- Nengzhong Wang (ORCID: https://orcid.org/0000-0003-1690-7611)
- Zhiyue Li (ORCID: https://orcid.org/0000-0001-9437-1002)
- Hui Qin Yao (ORCID: https://orcid.org/0000-0002-4450-8602)
- Dan Xiong
- Nianyu Huang (ORCID: https://orcid.org/0000-0003-4483-160X)
- Linxuan Li (ORCID: https://orcid.org/0000-0001-9836-1442)
- Sen Zhang (ORCID: https://orcid.org/0009-0003-7623-8568)
Institutions
- China Three Gorges University (CN)
Publication Details
- Journal
- The Journal of Organic Chemistry
- Published
- 2025-04-23
- DOI
- https://doi.org/10.1021/acs.joc.4c03159
- Citations
- 2
- Primary Topic
- Synthetic Organic Chemistry Methods
- Type
- article
- Field-Weighted Citation Impact
- 1.87
Funders
- Natural Science Foundation of Yichang City
- National Natural Science Foundation of China
- Higher Education Discipline Innovation Project