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Synthesis 2005(5): 798-803
DOI: 10.1055/s-2005-861814
DOI: 10.1055/s-2005-861814
PAPER
© Georg Thieme Verlag Stuttgart · New York
The Metalation of 1- and 2-(Trifluoromethyl)naphthalenes: Noteworthy Site Selectivities
Further Information
Received
13 October 2004
Publication Date:
09 February 2005 (online)
Publication History
Publication Date:
09 February 2005 (online)
Abstract
This article provides insight into the various factors by which electronegative substituents affect the kinetic acidity of arenes and, more specifically, naphthalenes. Both 1- and 2-(trifluoromethyl)naphthalenes were consecutively treated with an organometallic or lithium dialkylamide-type base and carbon dioxide. Due to single electron-transfer triggered side reactions, the yields of (trifluoromethyl)naphthoic acids were moderate to poor. 1-(Trifluoromethyl)naphthalene was exclusively attacked at the 2-position as expected. The 2-isomer reacted with tert-butyllithium in the presence of potassium tert-butoxide solely at the 1-position, but with sec-butyllithium in the presence of N,N,N′,N′-tetramethylethylenediamine concomitantly at the 3- and 4-positions. Authentic samples of the key acids 1, 4, 5 and 6 were prepared based on independent, unambiguous methods.
Key words
metalations - metal coordination - regioselectivity - superbases - (trifluoromethyl)naphthalenes - (trifluoromethyl)naphthoic acids
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