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Enantiopure Double‐Helical Phenylene Ethynylene Cyclophynes with the 2,2′‐Binaphthyl Template
Author(s) -
An DeLie,
Zhang YingJun,
Chen Qiang,
Zhao WenYing,
Yan Hong,
Orita Akihiro,
Otera Junzo
Publication year - 2007
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.200700149
Subject(s) - enantiopure drug , phenylene , arylene , ab initio , chirality (physics) , crystallography , acetylene , ring (chemistry) , chemistry , spectral line , ab initio quantum chemistry methods , connection (principal bundle) , stereochemistry , materials science , computational chemistry , molecule , mathematics , physics , organic chemistry , enantioselective synthesis , geometry , catalysis , alkyl , chiral symmetry breaking , quantum mechanics , astronomy , quark , nambu–jona lasinio model , aryl , polymer
New types of enantiopure compounds were synthesized to gain better insight into the structural features of phenylene ethynylene cyclophynes. Besides the previously obtained meta ‐substituted arylene ethynylenes, 1 , ortho ‐connected phenylene ethynylene units were incorporated to give cyclophynes with ortho / meta and ortho / ortho connection modes, 2 and 3 . Furthermore, a diphenylethyne component was also accommodated in 4 . Both ab initio calculations and NMR spectra suggest a large amount of strain for 2 but less strain for 3 and 1 a , the latter having the smallest ring size among cyclophynes with the meta/meta connection mode. The CD spectra of 2 and 3 showed a characteristic shoulder at around 340 nm, similar to the case of 1 a . This implies that the aromatic acetylene bonds cross over each other in the double‐helical structure. These results indicate that chirality information is useful for probing the persistency of molecular shape.