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This chapter covers enzyme classes that are capable of catalysing reactions to form carbon–carbon bonds, including aldolases, hydroxynitrile lyases, thiamine-dependent lyases, terpene cyclases, carboxylases, Pictet–Spenglerases, P450 monooxygenase variants and methyltransferases. The chapter is divided into separate sections, each detailing the formation of carbon–carbon bonds by a specific enzyme class. Each section begins with a review of chemical methods of carrying out similar transformations, followed by a description of the enzyme class itself. The substrate scope of each enzyme class, including its chemo-, regio- and stereoselectivity, is discussed and a general mechanism for the enzyme-catalysed reaction is presented. This should give the reader a good understanding of when and how to carry out carbon–carbon bond forming reactions using enzymes.

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