Terpenoid synthase structures: a so far incomplete view of complex catalysis.
Terpenoid synthase structures: a so far incomplete view of complex catalysis.
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DOI：
10.1039/c2np20059g
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发表时间：
2012-10
影响因子：
11.9
通讯作者：
Peters RJ
中科院分区：
文献类型：
--
作者：
Gao Y;Honzatko RB;Peters RJ
萜类化合物天然产物的复杂性引起了人们极大的兴趣，特别是自从它们共同的（聚）异戊二烯基来源被发现以来。值得注意的是，这种复杂性的大部分来自于观察到的烃骨架结构的高度可变的环化和/或重排性质。实际上，至少在某些情况下，难以立即识别它们源自聚异戊二烯基前体。然而，这些不同的结构是通过连续延伸形成无环前体，最常见的是随后的环化和/或重排。引人注目的是，用于组装和多样化萜类骨架的反应共享共同的碳阳离子驱动机制，尽管初始碳阳离子产生的方式确实不同。已经从参与产生萜类烃主链的各种类型的酶中的每一种获得了至少代表性实例的高分辨率晶体结构。然而，虽然这肯定导致了一些见解的酶的结构-功能关系的延伸和简单的环化反应，我们的理解更复杂的环化和/或重排反应仍然有限。因此，在此讨论了一些选定的例子，以展示我们目前的理解、其局限性和潜在的前进方向。
The complexity of terpenoid natural products has drawn significant interest, particularly since their common (poly)isoprenyl origins were discovered. Notably, much of this complexity is derived from the highly variable cyclized and/or rearranged nature of the observed hydrocarbon skeletal structures. Indeed, at least in some cases it is difficult to immediately recognize their derivation from poly-isoprenyl precursors. Nevertheless, these diverse structures are formed by sequential elongation to acyclic precursors, most often with subsequent cyclization and/or rearrangement. Strikingly, the reactions used to assemble and diversify terpenoid backbones share a common carbocationic driven mechanism, although the means by which the initial carbocation is generated does vary. High-resolution crystal structures have been obtained for at least representative examples from each of the various types of enzymes involved in producing terpenoid hydrocarbon backbones. However, while this has certainly led to some insights into the enzymatic structure–function relationships underlying the elongation and simpler cyclization reactions, our understanding of the more complex cyclization and/or rearrangement reactions remains limited. Accordingly, selected examples are discussed here to demonstrate our current understanding, its limits, and potential ways forward.
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DOI：
10.1073/pnas.96.23.13062
发表时间：
1999-11-09
影响因子：
11.1
作者：
Burke, CC;Wildung, MR;Croteau, R
通讯作者：
Croteau, R
影响因子：
2.9
作者：
Cao, Rong;Zhang, Yonghui;Mann, Francis M.;Huang, Cancan;Mukkamala, Dushyant;Hudock, Michael P.;Mead, Matthew E.;Prisic, Sladjana;Wang, Ke;Lin, Fu-Yang;Chang, Ting-Kai;Peters, Reuben J.;Odfield, Eric
通讯作者：
Odfield, Eric
影响因子：
4.8
作者：
Burke, C;Croteau, R
通讯作者：
Croteau, R
影响因子：
4.8
作者：
Chang, Tao-Hsin;Guo, Rey-Ting;Liang, Po-Huang
通讯作者：
Liang, Po-Huang
影响因子：
2.9
作者：
Deligeorgopoulou, A;Allemann, RK
通讯作者：
Allemann, RK