Synthesis of Acetylenic Cyclophanes via Intramolecular Self-Assembly:  Evidence of Perfluorophenyl−Phenyl Quadrupole Interactions in the Solution State

Abstract

Reported herein is an example of a solution-state cross-coupling cyclization with an outcome mediated by perfluorophenyl-phenyl electrostatic interactions.

Shape‐Persistent Macrocycles Based on Acetylenic Scaffolding

“…Marsella and coworkers have reported SPM formation based on quadrupole enhanced self-assembly in solution (Scheme 6.22A) [86]. While solid-state packing based on aryl-perfluoroaryl interactions (Ar H -Ar F ) is a well-established supramolecular motif [87,88], it was unique to see these electrostatic interactions manifested in a solution-state cyclization formation of 97-99 and then 100 and 101.…”

Chiral Carbon‐rich Macrocycles and Cyclophanes

“…Marsella and coworkers exploited perfluorophenyl-phenyl quadrupole interactions to template the synthesis of a thiophene-containing cyclophane [44]. As shown in Scheme 6.14, when the oligomeric precursors 98-101 were treated with Sonogashira cross-coupling conditions, the mixed perfluorophenyl-phenyl cyclophane 102 was reproducibly achieved in greater yield than either of the symmetrical analogs 103 and 104.…”

Exploitation of Perfluorophenyl–Phenyl Interactions for Achieving Difficult Macrocyclizations by Using Ring‐Closing Metathesis

“…[12] Surprisingly, relatively little use of these interactions in catalysis has been demonstrated, despite the tremendous utility of intramolecular p-p interactions in synthetically useful face-selective transformations. [13] A sole example of such quadrupolar interactions in the solution state was previously observed by Marsella et al, [14] which is in contrast to p-cation-arene interactions, whose applicability in the solution state was recently demonstrated by Yamada and Morita for the face-selective addition of nucleophiles to pyridines. [15] Herein, we report the development of a strategy that exploits quadrupolar perfluorophenyl-phenyl interactions, analogous to p-cation-arene interactions, for the construction of macrocycles.…”

“…The [13]paracyclophane 11 was produced in 57 % yield, whereas substitution of the pentafluorobenzyl ester for a methyl ester produced only dimeric products under identical conditions (entry 5). Although the corresponding benzyl ester of diene 12 yields the monomeric [14]paracyclophane in 51 % yield, substitution for a pentafluorobenzyl ester provided an increased yield of 63 % (entry 6). When the site of metathesis was moved closer to the aromatic core, the yield of macrocyclization decreased to provide 15 in 36 % yield (entry 7).…”