標題: [2.2.2.2](2,7)-1-Bromonaphthalenophane from a Desymmetrized Building Block Bearing Electrophilic and Masked Nucleophilic Functionalities
作者: Cai, Guangke
Chatterjee, Shreyam
Hisaki, Ichiro
Tobe, Yoshito
應用化學系
Department of Applied Chemistry
關鍵字: cyclophanes;stereochemistry;conformation analysis;cyclization;nucleophilic substitution
公開日期: 1-Mar-2019
摘要: 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 C-2 conformation with anti,anti,anti orientation of the C-Br bonds at least as a major component in crystal.
URI: http://dx.doi.org/10.1002/hlca.201800242
http://hdl.handle.net/11536/151618
ISSN: 0018-019X
DOI: 10.1002/hlca.201800242
期刊: HELVETICA CHIMICA ACTA
Volume: 102
Issue: 3
起始頁: 0
結束頁: 0
Appears in Collections:Articles