Investing in entropy: the strategy of cucurbit[n]urils to accelerate the intramolecular Diels-Alder cycloaddition reaction of tertiary furfuryl amines.

ABSTRACT: Cucurbit[n]urils, renowned for their host-guest chemistry, are becoming versatile biomimetic receptors. Herein, we report that cucurbit[7]uril (CB[7]) accelerates the intramolecular Diels-Alder (IMDA) reaction for previously elusive and unreactive tertiary N-methyl-N-(homo)allyl-2-furfurylamines by up to 4 orders of magnitude under mild conditions. Using ¹H NMR titrations and ITC experiments, we characterize the dissimilar thermodynamic and kinetic properties of the complexes. We also determine the activation parameters (ΔG ^≠, ΔH ^≠ and ΔS ^≠) leading to the transition state of the IMDA reactions, both in the bulk and included in CB[7], to shed light on the key role of the receptor on the acceleration obser

SUBMITTER: de la Vega-Hernandez K 

PROVIDER: S-EPMC11168187 | biostudies-literature | 2024 Jun

REPOSITORIES: biostudies-literature