Discovery and Theoretical Studies of Nonenzymatic Polyketide Dimerizations of Chaetophenols
Nonenzymatic reactions sometimes construct complex structures observed in natural products, showing us unique chemical reactions. In our exploration of natural products, we identified a novel type of isochromene-derived polyketide dimer <b>7</b> with a 6/6/6/6/6 five-ring system from <i>Chaetomium indicum</i> along with several new related polyketides. We demonstrated that isochromene <b>6</b> and its oxidized derivative <b>8</b> undergo nonenzymatic dimerization under acidic conditions to give <b>7</b>. Furthermore, density functional theory (DFT) calculations revealed the dimerization pathways, suggesting that the acidity (reaction condition) and <i>O</i>-prenylation are key factors in determining reaction mode.
Authors
- Takashi Yamamoto (ORCID: https://orcid.org/0000-0001-9586-6584)
- Taro Ozaki (ORCID: https://orcid.org/0000-0002-4673-4478)
- Junichiro Kanazawa (ORCID: https://orcid.org/0000-0001-6227-0864)
- Hiroto Matsui (ORCID: https://orcid.org/0000-0003-3588-8751)
- Hajime Sato (ORCID: https://orcid.org/0000-0001-5185-096X)
- Tohru Taniguchi (ORCID: https://orcid.org/0000-0002-4965-7383)
- Akihiro Sugawara (ORCID: https://orcid.org/0000-0003-1266-7497)
- Yui Masumoto
- Mamoru Watanabe (ORCID: https://orcid.org/0000-0002-5475-9544)
- Yohei Morishita (ORCID: https://orcid.org/0000-0001-8442-8642)
- Masanobu Uchiyama (ORCID: https://orcid.org/0000-0001-6385-5944)
- Teigo Asai (ORCID: https://orcid.org/0000-0002-8903-392X)
- Ayumi Watanabe (ORCID: https://orcid.org/0000-0001-9312-363X)
Institutions
- Tohoku University (JP)
- Hokkaido University (JP)
- Frontier Science Foundation (CH)
- The University of Tokyo (JP)
- Kumamoto University (JP)
Publication Details
- Journal
- Organic Letters
- Published
- 2025-01-27
- DOI
- https://doi.org/10.1021/acs.orglett.4c04346
- Citations
- 3
- Primary Topic
- Microbial Natural Products and Biosynthesis
- Type
- article
- Field-Weighted Citation Impact
- 4.18
Funders
- Japan Agency for Medical Research and Development
- Japan Society for the Promotion of Science
- Japan Science and Technology Agency
- Core Research for Evolutional Science and Technology
- Advanced Low Carbon Technology Research and Development Program