Uncatalyzed and Chorismate Mutase Catalyzed Claisen Rearrangement of (Z)-9-Methylchorismic Acid

Article abstract of DOI:10.1021/jo00256a016

A synthesis of (-)- and (+/-)-(Z)-9-methylchorismic acid (3) is reported.The half-life for the uncatalyzed Claisen rearrangement of (+/-)-3 in H2O (pH 7.5, 30 deg C) is 5.7 h.Chorismate analogue (-)-3 was a modest substrate for chorismate mutase (chorismate mutase-prephenate dehydrogenase from E. coli): K_m = 4.0 mM, k_cat./k_uncat. = 4.2*10⁴.It was established that the enzyme-catalyzed Claisen rearrangement of (-)-3 proceeds through a chairlike transition state in similar fashion to the chorismate mutase catalyzed rearrangement of (-)-chorismic acid (1).