[2.2.2.2](2,7)-1-Bromonaphthalenophane from a Desymmetrized Building Block Bearing Electrophilic and Masked Nucleophilic Functionalities

Guangke Cai, Shreyam Chatterjee, Ichiro Hisaki, Yoshito Tobe*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

1 Scopus citations

Abstract

In search of 2,7-ethylene-bridged naphthalenophanes with desymmetrized naphthalene cores as inherently chiral cyclophanes, nucleophilic substitution of 1-bromo-7-(bromomethyl)-2-[(trimethylsilyl)methyl]naphthalene, a desymmetrized building block bearing an electrophilic group (CH2Br) and a masked nucleophilic functionality (CH2TMS) which can be activated by fluoride anion, was examined. As a result, in contrast to the case of parent naphthalenophanes wherein the smallest [2.2]naphthalenophane was obtained as the major product, only [2.2.2.2](2,7)-1-bromonaphthalenophane was obtained albeit in low yields, whereas the corresponding [2.2]- or [2.2.2]naphthalenophanes were not obtained. Though the [2.2.2.2]-1-bromonaphthalenophane can adopt four idealized geometries of different symmetry, among which three are inherently chiral, theoretical calculations predict that three conformers have almost equal energy and may equilibrate in solution. The X-ray crystallographic study shows that it adopts a C2 conformation with anti,anti,anti orientation of the C−Br bonds at least as a major component in crystal.

Original languageEnglish
Article numbere1800242
JournalHelvetica Chimica Acta
Volume102
Issue number3
DOIs
StatePublished - 1 Mar 2019

Keywords

  • conformation analysis
  • cyclization
  • cyclophanes
  • nucleophilic substitution
  • stereochemistry

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