par Dussart, Alexia 
;Lengelé, Sébastien ;Jabin, Ivan ;Lavendomme, Roy
Référence Organic chemistry frontiers, 13, 17, page (5559–5567)
Publication Publié, 2026-08-25
;Lengelé, Sébastien ;Jabin, Ivan ;Lavendomme, Roy Référence Organic chemistry frontiers, 13, 17, page (5559–5567)
Publication Publié, 2026-08-25
Article révisé par les pairs
| Résumé : | Pillar[6]arenes exhibit highly valuable host–guest properties owing to their larger cavity relative to the widely studied pillar[5]arenes, yet their broader utilization has been impeded by longstanding challenges in selective and reproducible synthesis. Here, we report a general and efficient templated macrocyclization strategy based on the in situ formation of the Lewis adduct DABCO·2BF3. The remarkable structural complementarity between this hexagonal template and the pillar[6]arene cavity, reinforced by strong CH–π interactions, drives highly selective formation of pillar[6]arenes under BF3·Et2O catalysis in common chlorinated solvents. Under optimized conditions, dodecaethoxy-pillar[6]arene P[6]OEt is obtained in up to 77% yield on gram scale, and the protocol can be readily scaled to multigram quantities without chromatography purification. The method is applicable to a range of monomers bearing saturated alkyl chains and provides straightforward access to the key precursor P[6]OHvia dealkylation. Beyond its practical advantages, this work constitutes the first example of macrocyclization templated by a Lewis adduct. By overcoming critical limitations in selectivity, reproducibility, and scalability, this strategy offers an efficient solution for pillar[6]arene synthesis, opening new avenues for application developments. |
