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. Author manuscript; available in PMC: 2023 Apr 9.
Published in final edited form as: J Am Chem Soc. 2022 Mar 15;144(12):5214–5225. doi: 10.1021/jacs.2c00224

Figure 7.

Figure 7.

Biocatalytic strategies for intermolecular Diels–Alder reactions. (a) Artificial Diels–Alderases can be engineered by anchoring a metal cofactors into an enzyme cavity, training catalytic antibodies against a target transition state mimic, or computation design. (b) A bifunctional Diels–Alderase in the biosynthesis of neosetophomone B (54) catalyzes both the dehydration to form diene 53 and a [4+2] cycloaddition. (c) A stand-alone natural Diels–Alderase that catalyzes a concerted, intermolecular [4+2] cycloaddition was first discovered in the biosynthesis of chalcomoracin (57).