Diels-Alder reactions are among the most powerful synthetic transformations to construct complex natural products. Despite that increasing of enzymatic intramolecular Diels-Alder reactions have been discovered, natural intermolecular Diels-Alderases are rarely described. Here, we report an intermolecular hetero-Diels-Alder reaction in the biosynthesis of tropolonic sesquiterpenes and functionally characterize EupfF as the first fungal intermolecular hetero-Diels-Alderase. We demonstrate that EupfF catalyzed the dehydration of a hydroxymethyl-containing tropolone () to generate a reactive tropolone -quinone methide () and might further stereoselectively control the subsequent intermolecular hetero-Diels-Alder reaction with (1,4,8)-humulenol () to produce enantiomerically pure neosetophomone B (). Our results reveal the biosynthetic pathway of and expand the repertoire of activities of Diels-Alder cyclases.
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| http://dx.doi.org/10.1021/jacs.9b06592 | DOI Listing |
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