Selective Protection and De-protection of Phenolic Hydroxy Groups of Naringenin
XiaolongHuandGuo-ChunZhou
Abstract
Naringenin (1, Scheme 1) is a flavanone belonging to a part of a huge group of bioactive polyphenols. In order to selectively modify desired phenol/s, in this study, we developed some methods for selective protections of three hydroxy groups of 1. The 1st method is to silylate two hydroxy groups of 1 and then selectively de-protect the silylation product followed by site-selective acetylation, or site-selective silylation of 7-OH and then acetylation of 4’-OH. The 2nd synthetic method was started from triacetyloxylated naringenin (10), which was conducted in specific solvents to remove the distinctive acetyl protection by TFA, TsOH or imidazole. After protection of 4’,5-dihydroxynaringenin (12) by TBS at 7-OH to form 7-t-butyldimethylsilyloxy-4’,5-diacetyloxynaringenin (13), in the 3rd method, 4’-OAc or 5-OAc of 13 was selectively de-protected under acidic conditions to afford 4’-OH-5-OAc-7-OTBS naringenin (14) or 4’-OAc-5-OH-7-OTBS naringenin (6) as mixed protection derivatives. These methods have the advantages of mild reaction conditions, easily handled reagents and satisfactory yields.