硫醇加成/氧化构建具稳定阻转异构体的萘醌化合物

Synthesis of Naphthoquinone Compounds with Stable Axial Chirality by Addition/Oxidation of Mercaptans

轴手性是自然界的本征特性之一,在有机化学和药物化学研究中具有重要意义。醌类化合物广泛存在于天然产物、药物和其他功能性分子中,对构建含稳定阻转异构体的醌类化合物有重要研究价值。(1,2′-联萘)-1′,4′-二酮为一类含有C—C手性轴的化合物,但与常见的2,2′-双取代的1,1′-联萘不同,其手性轴的旋转能垒较小,室温下构型不稳定,故通过简单高效反应构建具稳定阻转异构体的1,2′-联萘醌是一项有吸引力的课题。本文以不同位阻取代的(1,2′-联萘)-1′,4′-二酮为底物,Cu(OAc)_(2)为助氧剂,EtOH为溶剂,在Et_(3)N的作用下,通过硫醇的加成/氧化反应直接构建了一系列具有稳定阻转异构体的联萘醌衍生物,共经^(1)H NMR,^(13)C NMR和HR-MS表征。

Axial chirality is one of the intrinsic properties of nature and has important significance in organic and medicinal chemistry.Quinone compounds are widely found in natural products,pharmaceuticals,and other functional molecules.Therefore,constructing quinone compounds with stable chiral axes is an important project.[1,2′-binaphthalene]-1′,4′-dione is a class of compounds containing a C-C chiral axis.However,unlike the common 2,2′-disubstituted 1,1′-binaphthalene,their chiral axes have a low rotational energy barrier,and the configuration is unstable at room temperature.Therefore,constructing[1,2′-binaphthalene]-1′,4′-dione with stable configuration through simple and efficient reactions is an attractive topic.In this work,a series of naphthoquinone derivatives with stable chiral axes were constructed by the addition/oxidation reaction of mercaptan with different substituted[1,2′-binaphthalene]-1′,4′-diones under the catalysis of triethylamine and Cu(OAc)_(2).The structures of all compounds were characterized by^(1)H NMR,^(13)C NMR,and HR-MS.