Premium
Novel Intramolecular Cyclization of 2‐(Buta‐1,3‐dienyl)benzyl Anions to 6,7(9)‐Dihydro‐5 H ‐benzocycloheptenyl Anions Leading to Successive Formation of 1,2‐Dihydrocyclopropa[ a ]naphthalenes
Author(s) -
Saitoh Hisashi,
Ijuin Hisako K.,
Watanabe Nobuko,
Matsumoto Masakatsu
Publication year - 2013
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.201200653
Subject(s) - chemistry , intramolecular force , nucleophilic substitution , medicinal chemistry , benzene , nucleophile , stereochemistry , intramolecular reaction , ion , organic chemistry , catalysis
When treated with LiN i Pr 2 (LDA) at −78°, 1‐[(methylsulfanyl)methyl]‐2‐[(1 Z ,3 E )‐4‐phenylbuta‐1,3‐dien‐1‐yl]benzene easily cyclized to form benzocycloheptenyl anion, which successively underwent intramolecular nucleophilic substitution to give a cyclopropanaphthalene. Similar LDA‐mediated cyclization also occurred for 4‐phenyl‐ or 4‐methyl‐substituted 1‐[2‐(methoxymethyl)phenyl]buta‐1,3‐dienes to furnish the corresponding benzocycloheptenes and cyclopropanaphthalenes. A 4‐ tert ‐butyl analog also underwent LDA‐mediated cyclization to give a benzocycloheptene, but not a cyclopropanaphthalene.