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首页> 外文期刊>Journal of the American Chemical Society >Doubly Deuterium-Labeled Patchouli Alcohol from Cyclization of Singly Labeled [2-~2H_1] Farnesyl Diphosphate Catalyzed by Recombinant Patchoulol Synthase
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Doubly Deuterium-Labeled Patchouli Alcohol from Cyclization of Singly Labeled [2-~2H_1] Farnesyl Diphosphate Catalyzed by Recombinant Patchoulol Synthase

机译：重组广atch香酚合酶催化单标记[2-〜2H_1]法呢基二磷酸环化的双氘标记的广cho香醇。

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摘要

Incubations of isotopically pure [2-~2H_1](E,E)-farnesyl diphosphate with recombinant patchoulol synthase (PTS) from Pogostemon cablin afforded a 65:35 mixture of monodeuterated and dideuterated patchoulols as well as numerous sesquiterpene hydrocarbons. Extensive NMR analyses (~1H and ~(13)C NMR, ~1H homodecoupling NMR, HMQC, and ~2H NMR) of the labeled patchoulol mixture and comparisons of the spectra with those of unlabeled alcohol led to the conclusion that the deuterium label was located at positions (patchoulol numbering system) C5 (both isotopomers, ca. 100%) and C12 (minor isotopomer, 30-35%), that is, an approximately 2:1 mixture of [5-~2H_1]- and [5,12-~2H_2]-patchoulols. Low-resolution FIMS analyses and isotope ratio calculations further corroborated the composition of the mixture as mainly one singly deuterated and one doubly deuterated patchoulol. From a mechanistic point of view, the formation of [5,12-~2H_2]patchoulol is rationalized through the intermediacy of an unknown exocyclic [7,10:1,5]patchoul-4(12)-ene (15-d_1), which could incorporate a deuteron at the C-12 position on the pathway to doubly labeled patchoulol. The corresponding depletion of deuterium content observed in the hydrocarbon coproducts, β-patchoulene and α-guaiene (55% d_0), identified the source of the excess label found in patchoulol-d_2. Comparison of the PTS amino acid sequence with those of other sesquiterpene synthases, and examination of an active site model, suggested that re-orientation of leucine 410 side chain in PTS might facilitate the creation of a 2-pocket active site where the observed deuteron transfers could occur. The retention of deuterium at C5 in the labeled patchoulol and its absence at C4 rule out an alternative mechanism involving two consecutive 1,2-hydride shifts and appears to confirm the previously proposed occurrence of a 1,3-hydride shift across the 5-membered ring. A new, semisystematic nomenclature is presented for the purpose of distinguishing the three different skeletal structures of the patchoulane sesquiterpenes.
机译：用Pogostemon cablin的重组广oul香酚合酶（PTS）进行同位素纯的[2-〜2H_1]（E，E）-法呢基二磷酸酯的孵育，可得到65:35的单氘代和二氘代广patch香醇以及多种倍半萜碳氢化合物的混合物。对标记的广patch香酚混合物进行广泛的NMR分析（〜1H和〜（13）C NMR，〜1H均解耦NMR，HMQC和〜2H NMR），并将光谱与未标记的醇进行比较，得出结论：氘标记为位于位置（广atch香酚编号系统）C5（均为同位素异构体，约100％）和C12（次异构体，为30-35％），即[5-〜2H_1]-和[5]的约2：1混合物，12-〜2H_2]-广atch香酚。低分辨率FIMS分析和同位素比计算进一步证实了混合物的成分，主要是一种单氘代和一种双氘代广patch香酚。从机理的角度来看，[5,12-〜2H_2]广atch香酚的形成是通过未知的环外[7,10：1,5]广atch香-4（12）-烯（15-d_1）的中间体合理化的，可以在双标记的广patch香酚的路径上的C-12位置掺入氘核。在烃副产物β-广atch烯和α-番石榴烯（55％d_0）中观察到的相应的氘含量减少，确定了广patch香酚-d_2中过量标记的来源。将PTS氨基酸序列与其他倍半萜合酶的氨基酸序列进行比较，并检查活性位点模型，这表明PTS中亮氨酸410侧链的重新取向可能会促进2口袋活性位点的形成，观察到的氘核转移可能发生。氘在标记的广patch香酚中在C5处的保留及其在C4处的不存在排除了涉及两个连续的1,2-氢化物转变的另一种机理，并且似乎证实了先前提议的在5元分子上发生1,3-氢化物转变的机制。环。为了区分广oul香倍半萜的三种不同的骨骼结构，提出了一种新的半系统命名法。

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  • 来源
    《Journal of the American Chemical Society》 |2010年第9期|p.2998-3008|共11页
  • 作者

    Juan A. Faraldos; Shuiqin Wu; Joe Chapped; Robert M. Coates;

  • 作者单位

    Department of Chemistry, University of Illinois, 600 South Mathews Avenue, Urbana, Illinois 61801rnCardiff School of Chemistry, Cardiff University, Cardiff, UK;

    rnDepartment of Plant and Soil Sciences, University of Kentucky, Lexington, Kentucky 40546-00991rnSapphire Energy, Inc., San Diego, CA;

    rnDepartment of Plant and Soil Sciences, University of Kentucky, Lexington, Kentucky 40546-00991;

    rnDepartment of Chemistry, University of Illinois, 600 South Mathews Avenue, Urbana, Illinois 61801;

  • 收录信息 美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
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