GEPHYROTOXINS, HISTRIONICOTOXINS AND PUMILIOTOXINS FROM NEOTROPICAL FROG DENDROBATES-HISTRIONICUS
GEPHYROTOXINS, HISTRIONICOTOXINS AND PUMILIOTOXINS FROM NEOTROPICAL FROG DENDROBATES-HISTRIONICUS
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DOI：
10.1002/hlca.19770600336
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发表时间：
1977-01-01
影响因子：
1.8
通讯作者：
KARLE, IL
中科院分区：
文献类型：
--
作者：
DALY, JW;WITKOP, B;KARLE, IL
从哥伦比亚蛙D. histrionicus，通过X射线晶体学测定。Gephyrotoxin（HTX-D）是一种新的三环生物碱[1 S，3aS，5aS，6S（Z），9aR，10 R]十二氢-6-（2-戊烯-4-基）吡咯并[1，2-a]喹啉-1-乙醇。二氢gephyrotoxin是一种次要的皮肤成分，含有一个6-（2，4-氨基）取代基。另外两种在结构上与组胺毒素相关的螺哌啶生物碱（6 R [6 α. [2S* （Z）]、[7. (Z)，8. alpha.]] 7-（1-丁烯-3-炔基）-2-（2-戊烯-4-炔基）-1-氮杂螺[5.5]十一烷-8-醇）。histrionicus：别二氢组胺毒素与组胺毒素的不同之处在于具有2-（4-戊炔基）-取代基，而别四氢组胺毒素（次要成分）具有2-（4-戊炔基）-和7-（1，3-丁二烯基）-取代基。从D. pumiliotoxin C中分离到3个结构相似的生物碱，即[2S，4aS，5 R，8aR]5-甲基-2-正丙基-顺式-十氢喹啉。表演者这些生物碱的分子量为195、223和269，分别具有2-丁基取代基、2-丙基和5-丙基取代基以及2-（3，4-戊烯-4-炔基）和5-（2-戊烯-4-炔基）取代基。最后一种化合物被氢化成分子量相同但其他性质不同的十二氢衍生物，其与由histrionicotoxin制备的真正的十二氢-8-脱氧-histrionicotoxin相同。Gephyrotoxin与histrionicotoxin和pumiliotoxin C相反，是一种毒蕈碱拮抗剂。
The structure and absolute configuration of a new acetylenic alkaloid gephyrotoxin isolated from skin extracts of the Colombian frog D. histrionicus, was determined by Roentgen-ray crystallography. Gephyrotoxin, previously referred to as HTX-D, is a novel tricyclic alkaloid, [1S,3aS,5aS,6S(Z),9aR,10R]dodecahydro-6-(2-penten-4-yl)pyrrolo[1,2-a]quinoline-1-ethanol. Dihydrogephyrotoxin, a minor skin constituent, contains a 6-(2,4-pentadienyl)substituent. Two further spiropiperidine alkaloids related in structure to histrionicotoxin, (6R[6.alpha.[2S*(Z)],[7.beta.(Z),8.alpha.]]7-(1-buten-3-ynyl)-2-(2-penten-4-ynyl)-1-azaspiro[5.5]undecan-8-ol), were isolated from D. histrionicus: allodihydrohistrionicotoxin which differs from histrionicotoxin in having a 2-(4-pentynyl)-substituent, while allotetrahydrohistrionicotoxin, a minor constituent, has 2-(4-pentynyl)- and 7-(1,3-butadienyl)-substituents. Three alkaloids related in structure to pumiliotoxin C, ([2S,4aS,5R,8aR]5-methyl-2-n-propyl-cis-decahydroquinoline), were isolated from D. histrionicus. These alkaloids, with MW of 195, 223, and 269, have, respectively, a 2-butylsubstituent, 2-propyl and 5-propyl-substituents, and 2-(3,4-pentadienyl) and 5-(2-penten-4-ynyl)-substituents. The last compound was hydrogenated to a dodecahydro-derivative identical in molecular weight, but not in other properties, with authentic dodecahydro-8-deoxy-histrionicotoxin, which was prepared from histrionicotoxin. Gephyrotoxin, in contrast to histrionicotoxin and pumiliotoxin C, is a muscarinic antagonist.