Sulfur Derivatives of the Natural Polyarsenical Arsenicin A: Biologically Active, Organometallic Arsenic–Sulfur Cages Related to the Minerals Realgar and Uzonite
作者:Di Lu、Sundaram Arulmozhiraja、Michelle L. Coote、A. David Rae、Geoff Salem、Anthony C. Willis、S. Bruce Wild、Shirine Benhenda、Valerie Lallemand Breitenbach、Hugues de Thé、Xiaoyi Zhai、Philip J. Hogg、Pierre J. Dilda
DOI:10.1021/om500829y
日期:2015.3.9
adamantane-type structure of the mineral arsenolite (As4O6), in which three of the oxygen atoms have been replaced by methylene groups to give an organometallic, arsenic–oxygen cage of C2 symmetry. Heating of a benzene solution of AsA with aqueous sodium sulfide produces, by reductive desulfurization of the intermediate sulfur analog (±)-2, the monosulfide cage (±)-4, which contains two As–As bonds and which
(±)-Arsenicin A(AsA),(±)-1,是第一个要分离的天然多砷化合物,具有矿物毒砂石(As 4 O 6)的金刚烷型结构,其中三个氧原子已经被被亚甲基取代,得到C 2对称的有机金属砷-氧笼。抗坏血酸与含水硫化钠的苯溶液的加热产生,由中间硫类似物的还原脱硫(±) - 2中,单硫化物笼(±) - 4,它包含两个AS-AS键和具有Ç 2 -相关的矿物雄黄手性笼状结构(α-作为4小号4)。在室温下反应,得到手性二硫化存在作为一对可分离非对映体,衍生物(±) -图3a和(±) - 3b中,其中的每一个包含单个AS-AS键和在结构上与所述矿物uzonite(如4 S 5)。-所述兰姆(±)的晶体结构4(±)和非对映体二硫化物-图3a和(±) - 3b中已经被确定。至于AsA,硫衍生物具有很强的紫外线吸收能力,可以在Chiralpak IA色谱柱上进行拆分。单硫笼(±)-4 它比AsA和目