Enzymes exercise impeccable control over chemoselectivity, site selectivity and stereoselectivity in reactions they mediate, such that we have witnessed a surge in the development of new biocatalytic methods. Although carbon–carbon (C–C) bonds are the central framework of organic molecules, biocatalytic methods for their formation have largely been limited to a select few lyase enzymes. Thus, despite several decades of research, there are not many biocatalytic C–C-bond-forming transformations at our disposal. This Review describes the suite of enzymes available for highly selective, biocatalytic C–C bond formation. We discuss each class of enzyme in terms of native activity, alteration of this activity through protein or substrate engineering, and its utility in abiotic synthesis.

酶对其介导的反应中的化学选择性、位点选择性和立体选择性有着无可挑剔的控制，因此我们见证了新生物催化方法的发展激增。尽管碳-碳（C-C）键是有机分子的中心框架，但其形成的生物催化方法在很大程度上仅限于精选的几种裂合酶。因此，尽管进行了数十年的研究，但我们可以利用的生物催化 C-C 键形成转化并不多。本综述描述了可用于高选择性、生物催化 C-C 键形成的酶套件。我们讨论每一类酶的天然活性、通过蛋白质或底物工程改变该活性及其在非生物合成中的用途。