Iridoid Sex Pheromone Biosynthesis in Aphids Mimics Iridoid-Producing Plants.
Iridoid Sex Pheromone Biosynthesis in Aphids Mimics Iridoid-Producing Plants.
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DOI：
10.1002/chem.202001356
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发表时间：
2021-04
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通讯作者：
S. J. Partridge;D. Withall;J. Caulfield;J. Pickett;R. Stockman;N. Oldham;M. Birkett
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文献类型：
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作者：
S. J. Partridge;D. Withall;J. Caulfield;J. Pickett;R. Stockman;N. Oldham;M. Birkett
生物合成（1 R，4aS，7S，7aR）-荆芥内酯醇（1）和植物中的（4aS，7S，7aR）-荆芥内酯（2）涉及环烯醚萜合酶（ISY），一种非典型还原性环化酶，其催化8-氧代香叶醛还原成（S）-8-氧代香茅醛的反应性烯醇，并催化该烯醇中间体的环化，非酶促或通过产生荆芥内酯醇的荆芥内酯醇相关的短链脱氢酶（NEPS）。在这项研究中，我们研究了在体内的生物合成1和2在豌豆蚜，Acyrthosiphon豌豆，使用库的同位素标记的单萜作为分子探针。从香叶醇和橙花醇合成的氘标记的探针的局部应用导致产生2 H4 -内半缩醛1和2 H4 -内酯2。然而，使用由（S）-香茅醇合成的标记探针，氘掺入并不明显。这些结果表明，环烯醚萜类化合物的生物合成在动物，特别是蚜虫，可能遵循一个广泛类似的路线，其特点为植物。
Biosynthesis of (1R,4aS,7S,7aR)-nepetalactol (1) and (4aS,7S,7aR)-nepetalactone (2) in plants involves iridoid synthase (ISY), an atypical reductive cyclase that catalyses the reduction of 8-oxogeranial into the reactive enol of (S)-8-oxocitronellal, and cyclization of this enol intermediate, either non-enzymatically or by a nepetalactol-related short chain dehydrogenase enzyme (NEPS) that yields the nepetalactols. In this study, we investigated the biosynthesis in vivo of 1 and 2 in the pea aphid, Acyrthosiphon pisum, using a library of isotopically-labelled monoterpenoids as molecular probes. Topical application of deuterium-labelled probes synthesized from geraniol and nerol resulted in production of 2 H4 -lactol 1 and 2 H4 -lactone 2. However, deuterium incorporation was not evident using labelled probes synthesized from (S)-citronellol. These results suggest that iridoid biosynthesis in animals, specifically aphids, may follow a broadly similar route to that characterised for plants.