Department of Chemical and Biological Engineering, University of Wisconsin-Madison, 1415 Engineering Dr., Madison, WI, 53706, USA.
DOE Great Lakes Bioenergy Research Center, University of Wisconsin-Madison, 1552 University Ave, Madison, WI, 53726, USA.
ChemSusChem. 2020 Oct 7;13(19):5213-5219. doi: 10.1002/cssc.202001471. Epub 2020 Aug 25.
Catalytic strategies were developed to synthesize and release chemicals for applications in fine chemicals, such as drugs and polymers, from a biomass-derived chemical, 5-hydroxymethyl furfural (HMF). The combination of the diene and aldehyde functionalities in HMF enabled catalytic production of acetalized HMF derivatives with diol or epoxy reactants to allow reversible synthesis of norcantharimide derivatives upon Diels-Alder reaction with maleimides. Reverse-conversion of the acetal group to an aldehyde yielded mismatches of the molecular orbitals in norcantharimides to trigger retro Diels-Alder reaction at ambient temperatures and released reactants from the coupled molecules under acidic conditions. These strategies provide for the facile synthesis and controlled release of high-value chemicals.
发展了催化策略，以合成和释放化学物质，用于从生物质衍生化学品 5-羟甲基糠醛（HMF）中应用于精细化学品，如药物和聚合物。HMF 中的二烯和醛官能团的组合使得可以用二醇或环氧化物反应物催化合成缩醛化 HMF 衍生物，从而允许与马来酰亚胺进行 Diels-Alder 反应后可逆合成 norcantharimide 衍生物。缩醛基团的反向转化为醛，导致 norcantharimides 中的分子轨道失配，在环境温度下引发逆 Diels-Alder 反应，并在酸性条件下从偶联分子中释放出反应物。这些策略为高价值化学物质的简便合成和控制释放提供了可能。
