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Molecules 2015, 20(9), 15862-15880;

Synthesis of Phenolic Compounds by Trapping Arynes with a Hydroxy Surrogate

Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL 60607, USA
College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, Zhejiang, China
Author to whom correspondence should be addressed.
Academic Editor: Hiroto Yoshida
Received: 6 August 2015 / Revised: 23 August 2015 / Accepted: 24 August 2015 / Published: 31 August 2015
(This article belongs to the Special Issue Development and Application of Aryne Chemistry in Organic Synthesis)
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Trapping of arynes with various nucleophiles provides a range of heteroatom-functionalized arene derivatives, but the corresponding reaction with water does not provide phenol derivatives. Silver trifluroacetate (AgO2CCF3) can nicely solve this problem. It was found that in typical organic solvent, AgO2CCF3 readily reacts with arynes to generate trifluoroacetoxy organosilver arene intermediate, which, upon treating with silica gel, provides phenolic products. This protocol can be extended to the synthesis of α-halofunctionalized phenol derivatives by simply adding NBS (N-bromosuccinimides) or NIS (N-iodosuccinimides) to the reaction along with silver trifluroacetate, which provided α-bromo or α-iodophenol derivatives in good yield. However, the similar reactions with NCS (N-chlorosuccinimides) afforded only the protonated product instead of the expected α-chlorophenols derivatives. Interestingly, substrates containing silyl substituents on 1,3-diynes resulted in α-halotrifluoroacetates rather than their hydrolyzed product. Additionally, trapping the same arynes with other oxygen-based nucleophiles containing silver counter cation, along with NXS (N-halosuccinimides), generated α-halooxyfunctionalized products. View Full-Text
Keywords: aryne; bis-functionalization; halophenol; silver trifluoroacetate; regioselectivity aryne; bis-functionalization; halophenol; silver trifluoroacetate; regioselectivity

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Karmakar, R.; Ghorai, S.; Xia, Y.; Lee, D. Synthesis of Phenolic Compounds by Trapping Arynes with a Hydroxy Surrogate. Molecules 2015, 20, 15862-15880.

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