Next Article in Journal
Functionalization of Cyclodextrins with N-Hydroxyphthalimide Moiety: A New Class of Supramolecular Pro-Oxidant Organocatalysts
Next Article in Special Issue
Selective Halogen-Lithium Exchange of 1,2-Dihaloarenes for Successive [2+4] Cycloadditions of Arynes and Isobenzofurans
Previous Article in Journal
p38α MAPK and Type I Inhibitors: Binding Site Analysis and Use of Target Ensembles in Virtual Screening
Previous Article in Special Issue
Synthesis of Oxygen Heterocycles via Aromatic C-O Bond Formation Using Arynes
Article Menu

Export Article

Open AccessCommunication
Molecules 2015, 20(9), 15862-15880; doi:10.3390/molecules200915862

Synthesis of Phenolic Compounds by Trapping Arynes with a Hydroxy Surrogate

1
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL 60607, USA
2
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)
View Full-Text   |   Download PDF [889 KB, uploaded 31 August 2015]   |  

Abstract

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
Figures

Figure 1

This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

Supplementary material

Scifeed alert for new publications

Never miss any articles matching your research from any publisher
  • Get alerts for new papers matching your research
  • Find out the new papers from selected authors
  • Updated daily for 49'000+ journals and 6000+ publishers
  • Define your Scifeed now

SciFeed Share & Cite This Article

MDPI and ACS Style

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

Show more citation formats Show less citations formats

Related Articles

Article Metrics

Article Access Statistics

1

Comments

[Return to top]

Molecules EISSN 1420-3049 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top