A Chiral LC-MS Strategy for Stereochemical Assignment of Natural Products Sharing a 3-Methylpent-4-en-2-ol Moiety in Their Terminal Structures

2025 · doi:10.3762/bxiv.2025.41.v1
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The paper studied stereochemical assignment of the terminal 3-methylpent-4-en-2-ol (MPO) moiety, a common feature in certain polyketide natural products, where traditional reliance on computational NMR, ECD, and specific rotation may fail for some compounds. The authors developed an accurate and sensitive strategy combining chemical degradation, chemical synthesis, and chiral LC-MS analysis, and used it to determine the absolute configuration of capsulactone. A key caveat is that the method addresses MPO stereochemistry specifically, rather than providing a general solution for stereochemistry across all structural elements or all natural products. This paper does not explicitly discuss endometriosis or adenomyosis; it was included in the corpus via a keyword match in the upstream search index.

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Abstract

A terminal 3-methylpent-4-en-2-ol (MPO) moiety is a common structural feature in various polyketide natural products. Stereochemical assignments of this moiety have mainly relied on computational analyses of NMR, ECD, and specific rotation data. However, neither of these approaches can be applied to all compounds. In this study, we developed an accurate and sensitive method to determine the absolute configuration of the terminal MPO moiety by a combination of chemical degradation, chemical synthesis, and chiral LC-MS analysis. The applicability of this method was demonstrated through the stereochemical assignment of capsulactone ( 1 ).
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Materials

chemistry Medicinal and pharmaceutical chemistry Nano- and molecular-scale electronics Nano-biomaterials and bioscience Nanomagnetics Nanomaterials, thin films and nanointerfaces Nanomedicine Nanometrology and nanomechanics Nano-optics Nanopatterning, self-assembly and nanofabrication Nanostructures for energy and sensing applications Natural products chemistry Organo main group chemistry Other nanotechnology (unclassified) Other organic chemistry (unclassified) Photochemistry and photovoltaics Physical organic chemistry Supramolecular chemistry A terminal 3-methylpent-4-en-2-ol (MPO) moiety is a common structural feature in various polyketide natural products. Stereochemical assignments of this moiety have mainly relied on computational analyses of NMR, ECD, and specific rotation data. However, neither of these approaches can be applied to all compounds. In this study, we developed an accurate and sensitive method to determine the absolute configuration of the terminal MPO moiety by a combination of chemical degradation, chemical synthesis, and chiral LC-MS analysis. The applicability of this method was demonstrated through the stereochemical assignment of capsulactone (1).

Keywords

a terminal 3-methylpent-4-en-2-ol (MPO) moiety; p-nitrobenzoyl (PNB) ester; methyl-3-hydroxy-2-methylbutanoate; chemical degradation; chiral LC-MS analysis | Format: PDF | Size: 1.6 MB | Download | When a peer-reviewed version of this preprint is available, this information will be updated in the information box above. If no peer-reviewed version is available, please cite this preprint using the following information: Suo, R.; Irie, R.; Nakayama, H.; Ishimaru, Y.; Akama, Y.; Oikawa, M.; Itoi, S. Beilstein Arch. 2025, 202541. doi:10.3762/bxiv.2025.41.v1 Citation data can be downloaded as file using the "Download" button or used for copy/paste from the text window below. Citation data in RIS format can be imported by all major citation management software, including EndNote, ProCite, RefWorks, and Zotero. © 2025 Suo et al.; licensee Beilstein-Institut. This is an open access work licensed under the terms of the Beilstein-Institut Open Access License Agreement (https://www.beilstein-archives.org/xiv/terms), which is identical to the Creative Commons Attribution 4.0 International License (https://creativecommons.org/licenses/by/4.0). The reuse of material under this license requires that the author(s), source and license are credited. Third-party material in this work could be subject to other licenses (typically indicated in the credit line), and in this case, users are required to obtain permission from the license holder to reuse the material.

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