Isoprenyl diphosphate synthases (IDSs) catalyze condensation reactions of isoprene units to produce isoprenoids or terpenoids, the largest class of natural products on earth. IDSs are divided into trans- and cis-IDS superfamilies depending on the configuration of the resulting carbon–carbon double bonds. Compared with trans-IDSs, cis-IDS family members exhibit more variable active site structure and versatile function. The archetypal cis-IDSs are homodimers and produce linear isoprenoids via head-to-tail condensation. Recently, heterodimeric cis-IDSs containing a noncatalytic subunit that also belongs to the cis-IDS superfamily have been identified. Moreover, several cis-IDS-fold members have been found to produce nonlinear isoprenoids via “head-to-middle” condensation. In this Review, we summarize the structural features and catalytic mechanism of the versatile cis-IDS superfamily. This information provides important guidance for research regarding biosynthesis of important natural products and medical intermediates, cellular metabolism, and disease control.

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多功能顺式-异戊二烯基二磷酸合酶超家族成员在催化碳-碳键形成中的作用

异戊二烯基二磷酸合酶（IDS）催化异戊二烯单元的缩合反应，产生异戊二烯或萜类化合物，这是地球上最大的天然产物。入侵检测系统分为反式-和顺-ids超家族取决于所得到的碳-碳双键的构型。与反式-IDS相比，顺式-IDS家族成员具有更多的可变活性位点结构和多功能。原型顺式-IDS是同型二聚体，并通过头对尾缩合产生线性类异戊二烯。最近，异二聚体顺式-IDS包含一个非催化亚基，也属于顺式-IDS超家族已被鉴定。此外，已经发现几个顺式-IDS-折叠成员通过“头对中间”缩合产生非线性类异戊二烯。在这篇综述中，我们总结了通用顺式-IDS超家族的结构特征和催化机理。这些信息为重要的天然产物和医学中间体的生物合成，细胞代谢和疾病控制的研究提供了重要的指导。