Synthesis of Phenolic Compounds by Trapping Arynes with a Hydroxy Surrogate.
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.
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL 60607, USA. rkarma2@uic.edu.
Rajdip
R
Karmakar
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL 60607, USA. sghora2@uic.edu.
Sourav
S
Ghorai
College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, Zhejiang, China. xyz@wzu.edu.cn.
Yuanzhi
Y
Xia
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL 60607, USA. dsunglee@uic.edu.
Daesung
D
Lee
D015394:Molecular Structure; D019800:Phenol / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism; D014269:Trifluoroacetic Acid / Q000737:chemistry
D019800:Phenol; D014269:Trifluoroacetic Acid
aryne; bis-functionalization; halophenol; regioselectivity; silver trifluoroacetate