2025年3月26日出版的《自然》杂志发表了美国科学家的一项最新研究成果。来自伊利诺伊大学的Scott E. Denmark研究小组报道了天然己糖和戊糖在水中与铟催化烯丙基化。

在这里，该课题组研究人员报道了在水中无保护的碳水化合物的高产量烯丙基化，以催化量的金属铟和烯丙基硼酸或蒎烯醇酯（烯丙基Bpin）作为供体。醛己糖、氨基己糖、酮己糖和醛己糖在温和条件下均能高收率地烯化，金属铟是可回收和可再生的，且不损失催化活性。利用这些特点，通过对反应参数的贝叶斯优化，该工艺转化为可扩展的连续流合成1-烯丙基山梨醇，收率高，生产率高。

据介绍，碳水化合物是一种丰富、廉价和可再生的生物质原料，可能是可持续化学制造的基石，但缺乏利用这些原料的可扩展和环保的方法。例如，1-烯丙基山梨醇是聚丙烯澄清剂Millad NX 8000的基本组成部分，该澄清剂每年以多公吨规模生产，但目前的制造过程需要超化学计量量的tin。NX 8000添加剂占全球澄清聚丙烯市场的80%左右，在聚丙烯生产过程中，其浓度为0.01-1%，以提高其透明度和耐高温性，每年可生产300-30,000公吨。2022年聚丙烯的市场数量约为7901万吨（MMT），预计到2030年需求将增长近33%，达到1.05亿吨。澄清聚丙烯的成本和可持续性优势推动了这一需求，因此需要更多的澄清剂。

附：英文原文

Title: Catalytic allylation of native hexoses and pentoses in water with indium

Author: Adak, Tapas, Menard, Travis, Albritton, Matthew, Florit, Federico, Burke, Martin D., Jensen, Klavs F., Denmark, Scott E.

Issue&Volume: 2025-03-26

Abstract: Carbohydrates are an abundant, inexpensive and renewable biomass feedstock that could be a cornerstone for sustainable chemical manufacturing, but scalable and environmentally friendly methods that leverage these feedstocks are lacking. For example, 1-allyl sorbitol is the foundational building block for the polypropylene clarifying agent Millad NX 8000, which is produced on the multi-metric ton scale annually, but the manufacturing process at present requires superstoichiometric amounts of tin1,2. The NX 8000 additives dominate about 80% of the global clarified polypropylene market3 and are used in concentrations of 0.01–1% during polypropylene production to improve its transparency and resistance to high temperatures, translating to 300–30,000 metric tons annually. The market volume of polypropylene in 2022 was approximately 79.01 million metric tons (MMT), with demand expected to rise by nearly 33% to 105 MMT by 2030 (ref.4). The cost and sustainability benefits of clarified polypropylene are driving this demand, necessitating more clarifying agents5. Here we report a high-yielding allylation of unprotected carbohydrates in water using a catalytic amount of indium metal and either allylboronic acid or the pinacol ester (allylBpin) as donors. Aldohexoses, aminohexoses, ketohexoses and aldopentoses are all allylated in high yield under mild conditions and the indium metal is recoverable and reusable with no loss of catalytic activity. Leveraging these features, this process was translated to a scalable continuous synthesis of 1-allyl sorbitol in flow6 with high yield and productivity through Bayesian optimization of reaction parameters.

DOI: 10.1038/s41586-025-08690-z

Source: https://www.nature.com/articles/s41586-025-08690-z