Department of Chemistry, University of California, Davis , One Shields Avenue, Davis, California 95616, United States.
J Am Chem Soc. 2014 Feb 12;136(6):2450-63. doi: 10.1021/ja4106489. Epub 2014 Feb 3.
Quantum chemical calculations on the transformation of the bisabolyl cation into an array of sesquiterpenes (iso-γ-bisabolene, trichodiene, cuprenene, laurene, isochamigrene, chamigrene, chamipinene, sesquithujene, sesquisabinene, microbiotene, dunniene, cumacrene, isobazzanene, bazzanene, barbatene, widdradiene, and thujopsene) are described. The bisabolyl cation is the hub of a complicated web of carbocations involved in the construction of diverse and complex molecular architectures present in a large number of Nature's sesquiterpenoids. The results of quantum chemical calculations on the multitude of rearrangements described herein provide reasonable answers to several persistent mechanistic questions in the world of terpene biosynthesis and also provide examples of general reactivity principles for terpene-forming (and other) carbocation rearrangements.
本文描述了双环醇阳离子转化为一系列倍半萜烯（异-γ-双环醇、曲二烯、杯烯、劳烯、异坎烯、坎烯、香木兰烯、大根香叶烯、大根香叶二烯、微生物烯、杜尼烯、库马烯、异巴泽烯、巴泽烯、巴尔巴烯、威德雷二烯和土木香烯）的量子化学计算。双环醇阳离子是一个复杂的碳正离子网络的中心，这些碳正离子参与了大量天然倍半萜烯中存在的各种复杂分子结构的构建。本文中描述的多种重排的量子化学计算结果为萜类生物合成领域的几个持续存在的机制问题提供了合理的答案，也为萜类形成（和其他）碳正离子重排的一般反应性原则提供了实例。
