Synthesis of Phenolic Compounds by Trapping Arynes with a Hydroxy Surrogate

Molecules

Rajdip Karmakar¹  Sourav Ghorai¹  Yuanzhi Xia²  Daesung Lee¹ 

[1] Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL 60607, USA; E-Mails:;College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, Zhejiang, China; E-Mail:

关键词: aryne;    bis-functionalization;    halophenol;    silver trifluoroacetate;    regioselectivity;   

DOI  :  10.3390/molecules200915862

来源: mdpi

【 摘 要 】

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.

【 授权许可】

CC BY   
© 2015 by the authors; licensee MDPI, Basel, Switzerland.