SYNTHESIS OF [14,14-[H-2]2]-LINOLENIC ACID AND ITS USE TO CONFIRM THE PATHWAY TO 12-OXOPHYTODIENOIC ACID (12-OXOPDA) IN PLANTS - A CONSPECTUS OF THE EPOXYCARBONIUM ION DERIVED FAMILY OF METABOLITES FROM LINOLEIC AND LINOLENIC ACID HYDROPEROXIDES
SYNTHESIS OF [14,14-[H-2]2]-LINOLENIC ACID AND ITS USE TO CONFIRM THE PATHWAY TO 12-OXOPHYTODIENOIC ACID (12-OXOPDA) IN PLANTS - A CONSPECTUS OF THE EPOXYCARBONIUM ION DERIVED FAMILY OF METABOLITES FROM LINOLEIC AND LINOLENIC ACID HYDROPEROXIDES
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DOI：
10.1039/p19910000581
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发表时间：
1991-03-01
期刊：
影响因子：
--
通讯作者：
MORGAN, DO
中科院分区：
文献类型：
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作者：
CROMBIE, L;MORGAN, DO
采用乙炔法合成了[14，14-H-2（2）]-十八碳-9（Z），12（Z），15（Z）-三烯酸。同位素标记的酸被用来明确区分两种可能的途径形成12-氧代植二烯酸（12-oxoPDA）通过植物中的亚麻酶制剂：（a）经由衍生自丙二烯环氧化物的两性环丙烷的异面闭环的途径，（没有14，14-H-2的损失（2））和（B）类似于公认的哺乳动物前列腺素生物合成的途径（损失一个14-H-2）。在自然界中由亚油酸和亚麻酸形成的代谢产物的途径总结于方案3中。进入物种被认为是环氧碳正离子。质子的损失导致丙二烯-环氧化物，由此形成α-酮醇、γ-酮醇和12-氧代PDA。第二组产物（寇奈酸和寇奈酸、半缩醛、其相应的醛和环氧醇）不是通过丙二烯-环氧化物形成的。环氧-碳鎓离子可以作为环氧醇被捕获，或者通过乙烯基-氧鎓离子被水捕获而重排以形成半缩醛。或者，从环氧-碳钥离子或乙烯基-氧钥离子损失质子导致可内烯酸和可内烯酸。
Using acetylene methodology, a synthesis of [14,14-H-2(2)]-octadeca-9(Z),12(Z),15(Z)-trienoic acid is described. The isotopically marked acid is used to distinguish decisively between two possible pathways for the formation of 12-oxophytodienoic acid (12-oxoPDA) by flax enzyme preparation in plants: (a) a route via antarafacial ring closure of a zwitterion derived from an allene epoxide (no loss of 14,14-H-2(2)) and (b) a pathway resembling the accepted mammalian prostaglandin biosynthesis (loss of one 14-H-2). Pathways to metabolic products formed in Nature from linoleic and linolenic acid are summarised in Scheme 3. The entry species is considered to be the epoxy-carbonium ion. Loss of a proton leads to an allene-epoxide from which are formed the alpha-ketol, the gamma-ketol and 12-oxoPDA. A second group of products (colneleic and colnelenic acid, a hemiacetal, its corresponding aldehydes and an epoxy alcohol) are not formed via the allene-epoxide. The epoxy-carbonium ion can be trapped as an epoxy alcohol or rearranged via a vinyl-oxonium ion with capture by water to form a hemiacetal. Alternatively, loss of a proton from the epoxy-carbonium ion or vinyl-oxonium ion leads to colneleic and colnelenic acid.