This paper describes the first synthesis of 3-methylcalix[4]arene, an inherently chiral mol. which can be readily functionalized. The procedure involves hydromethylation of the readily available 4-bromo-3-methylphenol followed by dehydrative cyclization with TiCl4 to give 4-bromo-3-methylcalix[4]arene. Debromination proceeds in near quant. yield to give the targeted 3-methylcalix[4]arene-25,26,27,28-tetrol. 3-Methylcalix[4]arene undergoes reactions at the para position to give functionalized chiral calix[4]arenes in good to excellent yields. [on SciFinder(R)]
