Hong Young J, Tantillo Dean J
Department of Chemistry, University of California, Davis, One Shields Avenue, Davis, California 95616, USA.
Org Lett. 2006 Sep 28;8(20):4601-4. doi: 10.1021/ol061884f.
The mechanisms proposed for enzyme-catalyzed formation of the sesquiterpene natural product trichodiene consistently include a step involving a 1,4-hydride transfer. Using quantum chemical methods (B3LYP/6-31+G(d,p) and mPW1PW91/6-31+G(d,p)), we discovered two alternative pathways for transformation of the intermediate bisabolyl cation to the cuprenyl cation, one of which--a proton-transfer pathway--appears to be much more energetically favorable (by more than 10 kcal/mol) than the hydride transfer pathways usually proposed.
为酶催化形成倍半萜天然产物里那醇所提出的机制一直都包括一个涉及1,4-氢转移的步骤。使用量子化学方法（B3LYP/6-31+G(d,p)和mPW1PW91/6-31+G(d,p)），我们发现了中间体甜没药烯基阳离子转化为库普瑞烯基阳离子的两条替代途径，其中一条——质子转移途径——在能量上似乎比通常提出的氢转移途径更有利（超过10千卡/摩尔）。
