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The Journal of organic chemistry

Substitution of hydroxybiaryls via directed ortho-lithiation of N-silylated O-aryl N-isopropylcarbamates.


PMID 16122233

Abstract

[reaction: see text] Herein we report regioselective substitution reactions of a series of 2- and 3-hydroxybiaryls including BINOL via a new directed ortho-metalation procedure. O-Aryl N-isopropylcarbamates, conveniently prepared from phenols and isopropyl isocyanate, are temporarily and in situ N-protected by means of silyl triflates to form stable intermediates for low temperature lithiation reactions using butyllithium/TMEDA in diethyl ether. The resulting aryllithiums are efficiently substituted by a wide range of electrophilic reagents to afford functionalized biaryls in high yields. N-Desilylation already occurs during aqueous workup. The following deprotection of the urethanes to the corresponding phenols proceeds rapidly and in quantitative yields. Even sensitive substituents (e.g., CO2Me, CHO, SiMe3, I) in the products are preserved under mild alkaline conditions which have been established for carbamate ester cleavage. Furthermore, applications of ortho-substituted products in common cross-coupling reactions for further C-C bond formations are demonstrated.

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141070
Isopropyl isocyanate, ≥98%
C4H7NO