Metal-exchanged clays (M = Rh and Cu) catalyze effectively the reaction of methyl diazoacetate with various aldehydes, affording the corresponding β-keto esters in high yields. They have also been effective in the decomposition of methyl diazoacetate to form metallocarbenes which, in turn, successfully insert into X–H (X = N, O, S, CO2) bonds of a variety of amines, aldehydes, thiols and acids, thereby producing the corresponding esters.