Supramolecular Capsule Catalysis Enables the Exploration of Terpenoid Chemical Space Untapped by Nature

Abstract

Terpenes represent the largest and the most diverse class of natural compounds. This is remarkable as the whole variety is accessed from just a handful of highly conserved linear precursors. Modification of the cyclization precursors would enable a dramatic expansion of the accessible chemical space. However, natural enzymes do not enable us to tap into this potential, as they do not tolerate larger deviations from the prototypical substrate structure. Herein we report that supramolecular capsule catalysis enables facile access to diverse and novel terpenoid skeletons that formally can be traced back to C3-phenyl, benzyl, and homoprenyl derivatives of farnesol. Novel skeletons related to the presilphiperfolane core structure, as well as novel neoclovene derivatives were accessed efficiently in only four synthetic steps. Importantly, the products obtained carry functional groups that may be readily derivatized further.

Exploring the Glycosylation Reaction Inside the Resorcin[4]arene Capsule

“…Supramolecular capsule and cage catalysis – have been recently increasingly utilized to perform selective reactions that are difficult to perform with small-molecule catalysts. – We reported that the supramolecular hexameric resorcin[4]­arene capsule I (Figure A) – is able to catalyze the conversion of α-glycosyl halides into β-glycosides in high selectivity. , Several points are noteworthy about this methodology. (1) The capsular catalyst enabled the formation of β-pyranosides as well as β-furanosides from the respective α-configured donors under nearly identical reaction conditions (Figure C).…”