Quantum chemical dissection of the classic terpinyl/pinyl/bornyl/camphyl cation conundrum-the role of pyrophosphate in manipulating pathways to monoterpenes
Quantum chemical dissection of the classic terpinyl/pinyl/bornyl/camphyl cation conundrum-the role of pyrophosphate in manipulating pathways to monoterpenes
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DOI：
10.1039/c0ob00167h
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发表时间：
2010-01-01
影响因子：
3.2
通讯作者：
Tantillo, Dean J.
中科院分区：
文献类型：
--
作者：
Hong, Young J.;Tantillo, Dean J.
基于量子化学研究，提出了由香叶基二磷酸生成香叶基二磷酸的反应机理。虽然通常认为焦磷酸正戊酯是通过焦磷酸基团与仲正戊酯阳离子的结合产生的，但量子化学计算表明，正戊酯阳离子实际上不是最小值。相反，焦磷酸基团的协同攻击加上烷基转移可以从蒎基阳离子或异丙基阳离子产生异丙基二磷酸。这些反应的能量表面上的分叉途径的线索也被发现。特别值得注意的是，开发和验证了一个完全用量子化学处理的焦磷酸盐的大型模型。
Based on quantum chemical studies, mechanisms to form bornyl diphosphate from geranyl diphosphate are suggested. While bornyl diphosphate is usually proposed to be generated via combination of the pyrophosphate group with a secondary bornyl cation, quantum chemical computations indicate that the bornyl cation is actually not a minimum. Instead, concerted attack of the pyrophosphate group coupled with an alkyl shift could yield bornyl diphosphate from either the pinyl cation or the camphyl cation. Hints of bifurcating pathways on the energy surfaces for such reactions were also uncovered. Of particular note is the development and validation of a large model of the pyrophosphate counterion treated entirely with quantum chemistry.