Triacca, Marylise, Carl, Reens D., Hamish, Stephen and Lam, Kevin ORCID: https://orcid.org/0000-0003-1481-9212 (2025) eSpiro: a scalable and sustainable electrosynthetic route to Spiroketals via anodic oxidation of malonic acids. Green Chemistry. ISSN 1463-9262 (Print), 1463-9270 (Online) (doi:10.1039/D5GC01767J)

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Abstract

Spiroketals are important structural motifs found in natural products, pharmaceuticals, and agrochemicals. However, their synthesis often requires hazardous reagents and harsh conditions, limiting their accessibility. Here, we present eSpiro, a novel electrosynthetic method for the efficient and sustainable synthesis of spiroketals via anodic oxidation of malonic acids. This approach offers a metal- and mercury-freealternative to conventional acid-catalysed or transition metal-mediated cyclisations. The reaction proceeds through a sequential Hofer-Moest decarboxylation, followed by Brønsted acid-mediated cyclisation, achieving high yields with broad functional group tolerance. We further explore the reaction scope and demonstrate its scalability, achieving up to 98% yield in batch. Additionally, we investigate a flow electrolysis setup, highlighting key challenges such as substrate stability, in-line solvent system switch and gas evolution, while demonstrating preliminary success in integrating electrochemical oxidation with downstream acid-catalysed cyclisation. This work provides a practical and eco-friendly route to spiroketals, with potential for industrial applications in organic synthesis.

Item Type:	Article
Additional Information:	This article is part of the themed collection: Green Chemistry Emerging Investigators Series. - MP
Uncontrolled Keywords:	electrochemistry, electrosynthesis, spirocycle, acetals
Subjects:	Q Science > Q Science (General) T Technology > T Technology (General)
Faculty / School / Research Centre / Research Group:	Faculty of Engineering & Science Faculty of Engineering & Science > School of Science (SCI)
Last Modified:	04 Jun 2025 10:50
URI:	http://gala.gre.ac.uk/id/eprint/50640

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