Department of Chemistry, University of Cincinnati, Cincinnati, OH, USA.
Department of Chemistry, University of California, Riverside, CA, USA.
Nat Commun. 2021 Mar 25;12(1):1868. doi: 10.1038/s41467-021-22157-5.
It is very attractive yet underexplored to synthesize heterocyclic moieties pertaining to biologically active molecules from biomass-based starting compounds. Herein, we report an electrocatalytic Achmatowicz reaction for the synthesis of hydropyranones from furfuryl alcohols, which can be readily produced from biomass-derived and industrially available furfural. Taking advantage of photo-induced polymerization of a bipyridyl ligand, we demonstrate the facile preparation of a heterogenized nickel electrocatalyst, which effectively drives the Achmatowicz reaction electrochemically. A suite of characterization techniques and density functional theory computations were performed to aid the understanding of the reaction mechanism. It is rationalized that the unsaturated coordination sphere of nickel sites in our electrocatalyst plays an important role at low applied potential, not only allowing the intimate interaction between the nickel center and furfuryl alcohol but also enabling the transfer of hydroxide from nickel to the bound furfuryl alcohol.
将与生物质基起始化合物相关的杂环部分合成具有生物活性的分子，这是一个非常有吸引力但尚未得到充分探索的领域。在此，我们报告了一种电催化的 Achmatowicz 反应，用于从糠醇合成氢吡喃酮，糠醇可以很容易地从生物质衍生和工业上可获得的糠醛制备得到。利用双吡啶配体的光诱导聚合，我们展示了一种易于制备的异质化镍电催化剂，它可以有效地驱动 Achmatowicz 反应的电化学过程。我们采用了一系列的表征技术和密度泛函理论计算来帮助理解反应机理。合理的是，我们电催化剂中镍位的不饱和配体场在低施加电势下起着重要作用，不仅允许镍中心与糠醇之间的紧密相互作用，而且还能促进氢氧根从镍转移到结合的糠醇上。
