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Earth-Abundant Metal Catalysts for the Dehydrodecarbonylation of Carboxylic Acids to Olefins

John, A.; Miranda, M. O.; Ding, K.; Dereli, B.; Ortuño, M. A.; LaPointe, A. M.; Coates, G. W.; Cramer, C. J.; Tolman, W. B.
Organometallics 2016, 35, 2391 (doi:10.1021/acs.organomet.6b00415).

Combining high-throughput experimentation with conventional experiments expedited discovery of new first-row nickel catalysts for the dehydrodecarbonylation of the bio-derived substrates hydrocinnamic acid and fatty acids to their corresponding alkenes. Conventional experiments using a continuous distillation process (180 oC) revealed that catalysts comprised of NiII or Ni0 precursors (NiI2, Ni(PPh3)4) and simple aryl phosphine ligands were the most active. In the reactions with fatty acids, the nature of the added phosphine influenced the selectivity for α-alkene, which reached a maximum value of 94%. Mechanistic studies of the hydrocinnamic reaction using Ni(PPh3)4 as catalyst implicate a facile first turnover to produce styrene at room temperature, but deactivation of the Ni0 catalyst by CO poisoning occurs subsequently, as evidenced by the formation of a Ni(CO)(PPh3)3, which was isolated and structurally characterized. Styrene dimerization is a major side reaction. Analysis of the reaction mechanism using density functional theory supported catalyst regeneration along with alkene formation as the most energetically demanding reaction steps.