Rearrangement of Hydroxylated Pinene Derivatives to Fenchone Type Frameworks: Computational Evidence for Dynamically-Controlled Selectivity
Rearrangement of Hydroxylated Pinene Derivatives to Fenchone Type Frameworks: Computational Evidence for Dynamically-Controlled Selectivity
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DOI：
10.1021/jacs.8b05804
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发表时间：
2018-07-25
影响因子：
15
通讯作者：
Sarpong, Richmond
中科院分区：
文献类型：
--
作者：
Blumel, Marcus;Nagasawa, Shota;Sarpong, Richmond
以酸催化的Prins/Semipinacol重排反应合成了三环芳酮类骨架，该反应具有很高的产率和非对映选择性。选择性决定步骤的量子化学分析支持在过渡态结构周围存在一个非常平坦的势能面。这种过渡态结构似乎是双峰结构，即在动态控制下通过后过渡态分叉(PTSB)形成Fenchone类型的三环支架而不是竞争形成龙脑(樟脑型)骨架。
An acid-catalyzed Prins/semipinacol rearrangement cascade reaction of hydroxylated pinene derivatives that leads to tricyclic fenchone-type scaffolds in very high yields and diastereoselectivity has been developed. Quantum chemical analysis of the selectivity-determining step provides support for the existence of an extremely flat potential energy surface around the transition state structure. This transition state structure appears to be ambimodal, i.e., the fenchone-type tricyclic scaffolds are formed in preference to the competing formation of a bornyl (camphor-type) skeleton under dynamic control via a post-transition state bifurcation (PTSB).