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A considerably improved synthesis of β-ketoadipic esters(3) and (4)—important intermediates for the synthesis of natural products—has been accomplished as shown below. (1), R1[DOUBLE BOND]CH3, reacts preferentially at the substituted carbonyl function; this is the first example of regioselective addition of a nucleophile with CC linkage by the “Bürgi-Duntiz principle”.