Obtaining Protoanemonin through Selective Oxidation of D‐Fructose and 5‐(Hydroxymethyl)furfural in a Self‐catalysed Reaction,Asian Journal of Organic Chemistry

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Obtaining Protoanemonin through Selective Oxidation of D‐Fructose and 5‐(Hydroxymethyl)furfural in a Self‐catalysed Reaction
Asian Journal of Organic Chemistry ( IF 2.8 ) Pub Date : 2020-09-13 , DOI: 10.1002/ajoc.202000406
Diana Becerra ₁ , José J. Martínez ₂ , Luis A. Páez ₂ , Luisa F. Gutiérrez ₂ , Oscar H. Pardo Cuervo ₂ , Hugo A. Rojas ₂ , Gustavo P. Romanelli ₃ , Jaime Portilla ₄ , Juan-Carlos Castillo ₂

Affiliation

Although different ways of converting 5‐(hydroxymethyl)furfural (1) to various substrates with high value have been sought, few transformations have obtained building blocks that can be very useful in the area of fine chemistry. Herein, we report the synthesis of protoanemonin (5‐methylenefuran‐2(5H)‐one) from D‐fructose via compound (1), a versatile γ‐alkylidenebutenolide, using an efficient self‐catalysed process with formic acid, with high reaction performance and selectivity (up to 94% yield and 98% conversion from (1), while 28% yield from D‐fructose). This efficient and simple operational process involved a two‐phase aqueous‐organic system between chlorinated solvents (CH_xCl_y) and hydrogen peroxide as the initial oxidizing agent. The reaction presents a key cleavage in the 5‐hydroxymethyl moiety of (1), due to the Baeyer‐Villiger oxidation (BVO) process that generates formic acid in situ. Ultimately, DFF and HMF were successfully obtained in 80% and 98% yield, respectively, starting from D‐fructose and using Preyssler heteropolyacids as Brønsted acid catalysts under an atmosphere of oxygen in the absence of hydrogen peroxide.

中文翻译：

通过自催化反应中D-果糖和5-（羟甲基）糠醛的选择性氧化获得原烟碱

尽管已寻求将5-（羟甲基）糠醛（1）转化为具有高价值的各种底物的不同方法，但很少有转化方法获得了在精细化学领域中非常有用的结构单元。此，我们报告原白头翁素的合成（5-methylenefuran-2（5 ħ） -酮）经由化合物（d-果糖1），一种多功能γ -alkylidenebutenolide，利用与甲酸的高效的自催化过程中，具有高反应性能和选择性（从（1）高达94％的产率和98％的转化率，而D-果糖的产率为28％）。这种高效，简单的操作过程涉及氯化溶剂之间的两相有机有机体系（CH _x Cl_y）和过氧化氢作为初始氧化剂。由于Baeyer-Villiger氧化（BVO）原位生成甲酸的过程，该反应在（1）的5-羟甲基部分发生了关键裂解。最终，从D-果糖开始，在氧气气氛下，在没有过氧化氢的情况下，使用Preyssler杂多酸作为布朗斯台德酸催化剂，成功分别以80％和98％的收率成功获得DFF和HMF。

更新日期：2020-09-13

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