SYNTHESIS OF ARYL CLUSTER GLYCOSIDES BY CYCLOTRIMERIZATION OF 2-PROPYNYL CARBOHYDRATE-DERIVATIVES
SYNTHESIS OF ARYL CLUSTER GLYCOSIDES BY CYCLOTRIMERIZATION OF 2-PROPYNYL CARBOHYDRATE-DERIVATIVES
复制标题
DOI：
10.1021/jo00146a023
复制
发表时间：
1982-01-01
影响因子：
3.6
通讯作者：
SIDHU, RS
中科院分区：
文献类型：
--
作者：
KAUFMAN, RJ;SIDHU, RS
在某些情况下，被称为植物抗毒素的抗微生物剂的引发是由含有β-1,6和β-1,3-键的低聚葡聚糖单元引发的。研究了金属离子介导的合适2-丙炔基糖前体的环三聚化作为制备这些激发子分子的潜在结构类似物的方法。因此，使用八羰基二钴作为催化剂进行2-丙炔基葡糖苷的反应，得到三聚簇糖苷，产率为44%。类似地，由炔基前体制备其他芳基簇糖苷。一般来说，这些反应以高区域选择性进行，1,2,4 区域异构体优先于 1,3,5 区域异构体，比例为 9:1。六聚簇糖苷由双功能取代的炔烃环三聚产生。大豆子叶生物测定表明，芳基簇糖苷作为植物抗毒素诱导剂没有活性。
The elicitation of antimicrobial agents called phytoalexins is, in some cases, triggered by oligomeric glucan units containing .beta.-1,6 and .beta.-1,3-linkages. Metal ion mediated cyclotrimerization of suitable 2-propynyl sugar precursors was investigated as a method to prepare potential structural analogs of these elicitor molecules. Thus, reaction of the 2-propynyl glucoside using dicobalt octacarbonyl as catalyst, gave a trimeric cluster glycoside in 44% yield. Similarly prepared were other aryl cluster glycosides from alkynyl precursors. In general, these reactions proceeded with high regioselectivity favoring the 1,2,4 over the 1,3,5 regioisomer by a ratio of 9:1. Hexameric cluster glycosides resulted from the cyclotrimerization of bifunctionally substituted alkynes. The aryl cluster glycosides are inactive as phytoalexin elicitors, as shown by the soybean cotyledon bioassay.