中国红树植物木榄Bruguiera gymnorrhiza中新颖罕见多聚二硫大环化合物的结构研究

通过对采自湛江红树林植物木榄(Bruguiera gymnorrhiza)中化学成分的系统研究, 从中分离得到5个聚二硫化合物. 经现代波谱学分析(IR, ¹H NMR, ¹³C NMR, 2D NMR, MS等), 鉴定其中1个化合物是结构新颖的多聚二硫大环化合物, 命名为木榄八硫醇(neogymnorrhizol, 1), 该化合物是由4个重复的2-羟基-1,3-丙二硫醇基聚合而成的二十元大环分子; 此外还分离得到了4个已知聚二硫化合物, 它们分别为木榄六硫醇(gymnorrhizol, 2a)、新木榄二硫醇(bruguiesulfurol, 3)、木榄二硫醇(brugierol, 4)和异木榄二硫醇(isobrugierol, 5). 其中化合物3的立体化学结构经过X单晶衍射并与文献对照得以确定, 在此基础上重新对化合物4和5的核磁共振信息进行全归属; 同时修订了文献中对化合物4立体化学结构的表述. 探讨了聚二硫化合物可能的生物合成途径, 分析了化合物1～5可能的相互间的生源关系; 经体外生物活性测试研究发现, 化合物2a和3均对II型糖尿病靶标分子人蛋白酪氨酸磷酸酯酶(hPTP1B)具有显著的抑制活性.

Structural Studies on an Unusual Novel Macrocyclic Polydisulfide from the Chinese Mangrove Bruguiera gymnorrhiza

Chemical study on the mangrove Bruguiera gymnorrhiza collected from Zhanjiang has resulted in the isolation of an unusual novel macrocyclic polydisulfide, neogymnorrhizol (1), which possesses an un-precedented carbon skeleton characterized by a twenty-membered macrocycle that is composed of four repeated 1,3-dimercaptopropan-2-ol units, along with four known related compounds. The structure of the new compound 1 was determined by detailed spectroscopic data analysis (IR, ¹H NMR, ¹³C NMR, 2D NMR, MS, etc.). The known compounds, namely gymnorrhizol (2a), bruguiesulfurol (3), brugierol (4) and isobrugierol (5), were determined by either an X-ray diffraction analysis or comparison with the data reported in the literatures. A plausible biogenetic origin of these uncommon polydisulfides and their biogenetic relationship were also discussed. In bioassay, compounds 2a and 3 exhibited significant hPTP1B inhibitory activ-ity.