Lessons from 1,3-Hydride Shifts in Sesquiterpene Cyclizations
Lessons from 1,3-Hydride Shifts in Sesquiterpene Cyclizations
复制标题
DOI：
10.1002/anie.201608042
复制
发表时间：
2016-10-17
影响因子：
16.6
通讯作者：
Dickschat, Jeroen S.
中科院分区：
文献类型：
--
作者：
Rinkel, Jan;Rabe, Patrick;Dickschat, Jeroen S.
立体特异性标记的前体进行转换由七个细菌倍半萜环化酶，以调查其初始的1，10-环化-1，3-氢化物移位级联的立体化学。与已知的绝对配置的产品的酶表现出连贯的立体化学过程中，除了（-）--amorphene合酶，其中所获得的结果是更好地解释了最初的1，6-环化。之间的联系的绝对配置的产品和立体化学过程中的1，3-氢化物的位移，使分配的绝对配置的三个酶的产品，这是通过共同的副产物germacreneD-4-ol的绝对配置独立确认。
Stereospecifically labelled precursors were subjected to conversion by seven bacterial sesquiterpene cyclases to investigate the stereochemistry of their initial 1,10-cyclisation-1,3-hydride shift cascades. Enzymes with products of known absolute configuration showed a coherent stereochemical course, except for (-)--amorphene synthase, for which the obtained results are better explained by an initial 1,6-cyclisation. The link between the absolute configuration of the product and the stereochemical course of the 1,3-hydride shifts enabled assignment of the absolute configurations of three enzyme products, which were confirmed independently through the absolute configuration of the common byproduct germacreneD-4-ol.