Formation of Beyerene, Kaurene, Trachylobane, and Atiserene Diterpenes by Rearrangements That Avoid Secondary Carbocations

被引：74
作者：
Hong, Young J. [1 ]
Tantillo, Dean J. [1 ]
机构：
[1] Univ Calif Davis, Dept Chem, Davis, CA 95616 USA
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2010年 / 132卷 / 15期
基金：
美国国家科学基金会;
关键词：
ABIETADIENE SYNTHASE CATALYSIS; SITE-DIRECTED MUTAGENESIS; FIR ABIES-GRANDIS; (+)-COPALYL DIPHOSPHATE; 2-NORBORNYL CATION; GERANYLGERANYL DIPHOSPHATE; NONCLASSICAL CARBOCATIONS; LANOSTEROL BIOSYNTHESIS; INITIATED CYCLIZATION; ENZYMATIC CYCLIZATION;
D O I：
10.1021/ja9084786
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Quantum chemical calculations on carbocation intermediates encountered during the conversion of ent-copalyl diphosphate to the diterpenes beyerene, kaurene, trachylobane, and atiserene are described. Based on the results of these computations, it is suggested that previously proposed secondary carbocation intermediates are avoided. In some cases, complex rearrangements in which up to three alkyl or hydride shifting events are coupled into concerted processes are predicted to occur instead. The potential effects of electron-rich active site groups on the inherent reactivity of key carbocations are discussed, as are complex rearrangements coupled to deprotonation events. Based on computed electrostatic potential maps, it also is proposed that ammonium ions that were previously designed as mimics of several carbocations are actually better mimics of transition state structures for carbocation deprotonation.
引用
收藏
页码：5375 / 5386
页数：12
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