在四大麻素的生物合成中挖掘和隐藏的中间体的计算证据
Edyta M Greer1, Victor Siev1, Ayelet Segal1
1Department of Natural Sciences, Baruch College of the City University of New York, 17 Lexington Avenue, New York, New York 10010, United States.
Journal of the American Chemical Society
|April 22, 2022
概括
量子道对大麻酸转化为 (-) - 跨-Δ9-四大麻 (THC) 有显著影响. 这项研究揭示了道化对包括脱碳化在内的关键反应步骤的贡献率在19-76%.
科学领域:
- 量子化学
- 有机化学
- 计算化学
背景情况:
- 大麻酸转化为THC需要一个复杂的反应序列.
- 包括量子效应在内的反应机制对于大麻素研究至关重要.
研究的目的:
- 为了计算多维量子道化反应序列将大麻酸转化为THC.
- 阐明THC形成的机制,并确定关键的速度限制步骤.
主要方法:
- 使用了POLYRATE和GAUSSRATE计算软件.
- 使用B3LYP/6-31G (d,p) 级理论进行计算.
- 通过用甲基替换链来简化前体.
主要成果:
- 量子道对反应速率的贡献在293K之间为19%至76%.
- 在keto-enol分体化步骤中确定了一个"隐藏的中间体",只能通过零点能量考虑来检测.
- 预测可观测的动态同位素效应用于实验验证.
结论:
- 量子道在THC形成动力学中起着重要作用.
- 这种"隐藏的中间体"为反应路径的动态提供了新的见解.
- 动态同位素效应的实验验证是可行的,也是建议的.
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