Supplementary Figure 3: Decarboxylative and non-decarboxylative Claisen condensation reactions in biological systems.

Claisen condensations mediate the formation of carbon-carbon bonds (represented as a green, thick bond) between the α carbon of the extender unit and the carbonyl carbon of the primer. (a) The β-carboxyl group of the extender unit malonyl-CoA/ACP is released as CO2 during decarboxylative Claisen condensation with acetyl-CoA/ACP priming. Generation of malonyl-CoA/ACP requires the ATP-dependent carboxylation of acetyl-CoA. (b) Non-decarboxylative Claisen condensation directly utilizes acetyl-CoA for carbon elongation, thus circumventing ATP consumption.