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呋喃的光水解
作者:小柯机器人 发布时间:2026/1/16 14:53:05

近日,德国马克斯普朗克煤炭研究所Benjamin List团队研究了呋喃的光水解。这一研究成果发表在2026年1月15日出版的《科学》杂志上。

化学工业的去化石燃料化进程正因原料从石油向生物质的转变而加速。其中,生物基呋喃化合物处于核心地位——通过氧化或还原工艺可从中获得高价值平台化学品。相比之下,呋喃水解生成丁二醛(以及2-取代呋喃生成1,4-酮醛)这一概念上直接的非氧化还原水解反应,因其吸能特性与易发生聚合副反应,长期以来被认为难以实现。

研究组报道了通过光催化途径实现这种"上坡"式呋喃水解反应的方法,该过程涉及一个高张力的十元环1,6-二氧辛烷中间体。丁二醛及1,4-酮醛得以直接从呋喃类化合物获得。此外,糠醛衍生物可通过氧化还原增强的Piancatelli重排反应,转化为具有抗菌活性的天然产物(±)-土曲霉酮与(±)-表戊烯霉素。该方法被应用于常见工业精细化学品的非氧化还原合成路线,避免了生物基合成中典型的冗余氧化还原步骤。

附:英文原文

Title: The photohydrolysis of furans

Author: Nils Frank, Moreshwar B. Chaudhari, Markus Leutzsch, Benjamin Helmich-Paris, Paolo Cleto Bruzzese, Darryl Nater, Nils Nthling, Alexander Schnegg, Siegfried R. Waldvogel, Benjamin List

Issue&Volume: 2026-01-15

Abstract: The defossilization of the chemical industry is accelerated by the shift from petroleum- to biomass-based feedstocks. At the center stage are bioderived furans, from which valuable platform chemicals can be obtained exclusively through oxidative or reductive processes. By contrast, the conceptually straightforward redox-neutral hydrolysis of furan to succinaldehyde and 2-substituted furans to 1,4-ketoaldehydes has been considered unfeasible owing to their endergonicity and polymerization side reactivity. In this work, we report the realization of this uphill furan hydrolysis through photocatalysis involving a highly strained, 10-membered 1,6-dioxecine intermediate. Succinaldehyde, as well as 1,4-ketoaldehydes, can be directly obtained from furans. Additionally, furfural derivatives undergo redox-enhanced Piancatelli rearrangements, accessing antimicrobial natural products (±)-Terrein and (±)-epi-Pentenomycins. The methodology was applied to the redox-neutral production of common industrial fine chemicals, avoiding wasteful redox detours typical in biomass-based synthesis.

DOI: aec6532

Source: https://www.science.org/doi/10.1126/science.aec6532

期刊信息

Science:《科学》,创刊于1880年。隶属于美国科学促进会,最新IF:63.714
官方网址:https://www.sciencemag.org/
投稿链接:https://cts.sciencemag.org/scc/#/login