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Use of ZrO 2 /SiO 2 as asolid acid catalyst in the ringopening of biobased g-valerolactone with methanol in the gas phase leads to mixtures of methyl 2-, 3-, and 4-pentenoate (MP) in over 95 %selectivity,containing asurprising 81 %of M4P.This process allows the application of aselective hydroformylation to this mixture to convert M4P into methyl 5formyl-valerate (M5FV) with 90 %s electivity.T he other isomers remain unreacted. Reductive amination of M5FV and ring-closure to e-caprolactam in excellent yield had been reported before.T he remaining mixture of 2-and 3-MP was subjected to an isomerising methoxycarbonylation to dimethyl adipate in 91 %yield. Scheme 1. Routes to e-caprolactam from butadiene.