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Lewis Acid‐Catalyzed Ring‐Opening Functionalizations of 1,4‐Epoxy‐1,4‐dihydronaphthalenes
Author(s) -
Sawama Yoshinari,
Ogata Yuta,
Kawamoto Koichi,
Satake Hiroyuki,
Shibata Kyoshiro,
Monguchi Yasunari,
Sajiki Hironao,
Kita Yasuyuki
Publication year - 2013
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201200771
Subject(s) - chemistry , nucleophile , lewis acids and bases , epoxy , regioselectivity , moiety , catalysis , trimethylsilyl azide , lewis acid catalysis , trimethylsilyl cyanide , cyanide , azide , surface modification , ring (chemistry) , organic chemistry , combinatorial chemistry , medicinal chemistry
Since 1,4‐epoxy‐1,4‐dihydronaphthalenes are smoothly converted to 1‐naphthol derivatives via unstable cation intermediates formed by the acid‐catalyzed ring‐opening reaction of the 1,4‐epoxy moiety of 1,4‐epoxy‐1,4‐dihydronaphthalenes, their nucleophilic functionalization using the cation intermediates as an active species is extremely difficult. We have accomplished the Lewis acid‐catalyzed carbon‐carbon and carbon‐nitrogen bond formations associated with the ring‐opening of 1,4‐epoxy‐1,4‐dihydronaphthalenes using nucleophiles such as allyltrimethylsilanes, trimethylsilyl cyanide and trimetylsilyl azide, by using the stabilization effect of the cation intermediate based on the introduction of appropriate substituents into the bridgehead positions of 1,4‐epoxy‐1,4‐dihydronaphthalenes to give the corresponding unique and multifunctionalized naphthalene derivatives. The present reactions could provide excellent regioselective functionalization methods using unsymmetrical substrates, which are quite difficult to achieve using transition metal‐induced procedures.