Expanding Meroterpenoid Chemical Space Via Intermolecular Trapping of Cationic Cyclization Intermediates

Abstract

Meroterpenoids are a subclass of terpenes that consist of a nonterpene part, that is, in many cases, an aryl residue, linked to a terpene component. Their biosynthesis involves the attachment of the aryl group to the tail end of the acyclic terpene part, followed by terpene cyclization. Here we explore an alternative method for accessing meroterpenoids. The terpene cyclization is performed in the presence of arenes that trap key cationic intermediates in an intermolecular fashion. Our study demonstrates the feasibility of this approach that, to our knowledge, has not been reported before. It enables direct access to the novel meroterpenoid chemical space.

Keywords: Resorcin[4]arene catalysis; carbocation trapping; meroterpenoid synthesis; supramolecular catalysis.

1

(a) Typical biosynthetic pathway of meroterpene; (b) cyclization of caryophyllene alcohol 2 in capsule I in the presence of an external nucleophile; (c) self-assembly of resorcin[4]­arene into a hexameric capsule.

2

Derivatization options for furan 10.