In the current shortage of fossil reserves, the conversion of natural-product feedstocks into valuable synthetic chemicals has become crucial. In this line, catalytic deoxygenation processes hold promise to transform biomass-derived carboxylic acid derivatives into high-value linear α-olefins.<br/><br/>Herein we present a Pd-catalyzed decarbonylation reaction that converts fatty acid esters to linear α-olefins (LAOs). While the use of N-heterocyclic carbene ligands essentially produces the undesired internal alkene, bidentate phosphines significantly increase the selectivity to terminal olefins. In addition, the combination of both N-heterocyclic carbene and bidentate phosphine ligands yields high conversion and excellent selectivity. To understand this outcome we have studied the decarbonylation mechanism by computational means. DFT calculations point toward the bulkiness of the carbene and the denticity of the phosphine as key factors to control the alkene release (linear olefin) vs alkene isomerization (internal olefin) processes.

Mechanism of Pd-catalyzed decarbonylation of esters to linear α-olefins

253rd National Meeting (2017)

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