Graduate School of Agriculture, Hokkaido University, Sapporo, Japan.
School of Agriculture, Hokkaido University, Sapporo, Japan.
Biosci Biotechnol Biochem. 2021 Feb 18;85(2):215-222. doi: 10.1093/bbb/zbaa031.
Hinokitiol has a broad antibacterial activity against bacteria and fungi. While its biosynthetic pathway has been intensively studied, its dynamics in natural environments, such as biodegradation pathway, remain unclear. In this study, the authors report a direct deuterium labeling of hinokitiol as a traceable molecular probe to serve those studies. Hinokitiol was subjected to the H2-Pd/C-D2O conditions and deuterated hinokitiol was obtained with excellent deuteration efficiencies and in moderate yield. The 1H and 2H NMR spectra indicated that all ring- and aliphatic hydrogens except that on C-6 were substituted by deuterium. According to the substrate scope and computational chemistry, deuteration on tropolone ring was suggested to proceed via D+-mediated process, and which was supported by the results of the experiment with trifluoroacetic acid and Pd(TPP)4. On the other hand, the deuteration on aliphatic group was predicted to be catalyzed by Pd(II) species.
桧醇具有广谱的抗细菌和真菌活性。尽管其生物合成途径已得到深入研究，但在自然环境中的动态，如生物降解途径，仍不清楚。在这项研究中，作者报告了桧醇的直接氘标记，作为可追踪的分子探针来进行这些研究。桧醇在 H2-Pd/C-D2O 条件下进行处理，得到了具有优异的氘化效率和中等产率的氘代桧醇。1H 和 2H NMR 谱表明，除 C-6 上的氢以外，所有的环氢和脂肪氢都被氘取代。根据底物范围和计算化学，提示三羟甲基苯并呋喃环的氘化是通过 D+-介导的过程进行的，这一结果得到了三氟乙酸和 Pd(TPP)4 实验结果的支持。另一方面，脂肪族基团的氘化被预测是由 Pd(II)物种催化的。
