Theoretical study of the rearrangement reaction in bisorbicillinoid biosynthesis: insights into the molecular mechanisms involved (original) (raw)
* Corresponding authors
a Interdisciplinary Graduate School of Medicine and Engineering, University of Yamanashi, 4-4-37 Takeda, Kofu, Yamanashi 400-8510, Japan
E-mail: hsato@yamanashi.ac.jp
b PRESTO, Japan Science and Technology Agency, Kawaguchi, Saitama 332-0012, Japan
Abstract
Bisorbibutenolide and bisorbicillinolide are polyketide compounds with complex skeletons that are formed by the dimerization of sorbicillin. These compounds have long been of interest, with several reports of their biosynthesis, biological activity, and total synthesis. In this study, we theoretically investigated the detailed biosynthetic mechanism of the rearrangement reaction to form bisorbicillinolide. We showed that the presence of water molecules facilitates the intramolecular aldol reaction, determined the rate-limiting steps, and revealed that a cyclopropane intermediate is formed during the rearrangement process. Although computational chemistry has been widely applied to the carbocation chemistry present in terpene biosynthesis, it has seldom been used to investigate the carbonyl chemistry responsible for polyketide biosynthesis. This study shows that computational chemistry is a useful tool for studying anionic skeletal rearrangement reactions.
You have access to this article
Please wait while we load your content... Something went wrong. Try again?
Article information
DOI
https://doi.org/10.1039/D3OB00728F
Article type
Communication
Submitted
10 May 2023
Accepted
09 Jun 2023
First published
12 Jun 2023
Download Citation
Org. Biomol. Chem., 2023,21, 5366-5371
Author version available
Permissions
Theoretical study of the rearrangement reaction in bisorbicillinoid biosynthesis: insights into the molecular mechanisms involved
M. Nakano and H. Sato,Org. Biomol. Chem., 2023, 21, 5366DOI: 10.1039/D3OB00728F
To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.
If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.
If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.
Read more about how to correctly acknowledge RSC content.