埃斯皮罗:一种可扩展和可持续的电合成途径,通过丙二酸的阳极氧化产生螺旋酮

IF 9.3 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Green Chemistry Pub Date : 2025-06-03 DOI:10.1039/D5GC01767J
Marylise Triacca, Carl D. Reens, Hamish Stephen and Kevin Lam
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引用次数: 0

摘要

螺旋酮是天然产物、药品和农用化学品中发现的重要结构基序。然而,它们的合成往往需要危险的试剂和恶劣的条件,限制了它们的可及性。在这里,我们提出了一种新的电合成方法eSpiro,通过丙二酸的阳极氧化来高效和可持续地合成螺旋酮。这种方法为传统的酸催化或过渡金属介导的环化提供了一种无金属和无汞的替代方法。该反应通过一系列Hofer-Moest脱羧进行,然后是Brønsted酸介导的环化,从而获得高收率和广泛的官能团耐受性。我们进一步探索了反应范围,并证明了其可扩展性,批量产率高达98%。此外,我们还研究了一种流动电解装置,强调了衬底稳定性、在线溶剂系统切换和气体演化等关键挑战,并展示了将电化学氧化与下游酸催化循环相结合的初步成功。这项工作为螺旋酮提供了一条实用和环保的途径,在有机合成中具有工业应用潜力。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

eSpiro: A scalable and sustainable electrosynthetic route to spiroketals via anodic oxidation of malonic acids†

eSpiro: A scalable and sustainable electrosynthetic route to spiroketals via anodic oxidation of malonic acids†

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-free alternative 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, and also 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.

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来源期刊
Green Chemistry
Green Chemistry 化学-化学综合
CiteScore
16.10
自引率
7.10%
发文量
677
审稿时长
1.4 months
期刊介绍: Green Chemistry is a journal that provides a unique forum for the publication of innovative research on the development of alternative green and sustainable technologies. The scope of Green Chemistry is based on the definition proposed by Anastas and Warner (Green Chemistry: Theory and Practice, P T Anastas and J C Warner, Oxford University Press, Oxford, 1998), which defines green chemistry as the utilisation of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products. Green Chemistry aims to reduce the environmental impact of the chemical enterprise by developing a technology base that is inherently non-toxic to living things and the environment. The journal welcomes submissions on all aspects of research relating to this endeavor and publishes original and significant cutting-edge research that is likely to be of wide general appeal. For a work to be published, it must present a significant advance in green chemistry, including a comparison with existing methods and a demonstration of advantages over those methods.
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