Palladium Precatalysts for Decarbonylative Dehydration of Fatty Acids to Linear Alpha Olefins

Abstract

Transition-metal-catalyzed decarbonylative dehydration of even-numbered fatty acids to give valuable odd-numbered alpha olefins has so far been performed using approaches in which the catalyst is formed in situ. We show that well-defined Pd­(bis-phosphine) precatalysts eliminate the need for excess phosphine and selectively produce linear alpha olefins under mild conditions and with substantially increased turnover frequency (TOF) and substrate scope. In particular, the new precatalyst Pd­(cinnamyl)­Cl­(DPEPhos) (5) selectively converts substrates containing unprotected aliphatic-alcohol and amine functional groups to their corresponding linear alpha olefins.

Synthesis and characterization of a thermally crosslinkable polyolefin from oleic acid

“…The transformation of oleic acid to MO was performed according to previous reports . Pd‐catalyzed decarbonylative elimination afforded MO in good yield (70%).…”

“…The transformation of oleic acid to MO was performed according to previous reports. [13][14][15] Pd-catalyzed decarbonylative elimination afforded MO in good yield (70%). Since MO has both terminal and internal olefin moieties, to obtain a structurally defined polymer material, its polymerization should proceed stereoregularly and site selectively at the terminal olefin moiety.…”

“…Herein, we have introduced a chemical transformation of oleic acid to a novel polyolefin possessing an internal olefin moiety as a reactive functional group (Scheme 1). Since the conversion of oleic acid to (8Z)-1,-8-heptadecadiene (MO) via catalytic decarbonylative elimination has been reported, [13][14][15] we envisioned the site-specific polymerization of MO to obtain a new functional polyolefin (PO). The internal olefin moiety in PO can be converted to various functional groups.…”

The Manganese‐Catalyzed Cross‐Coupling Reaction and the Influence of Trace Metals

“…4‐Phenylbut‐1‐ene (5): 1 H NMR (400 MHz, CDCl 3 ): δ = 7.53–7.12 (m, 5 H), 5.88 (ddt, J = 16.9,10.2, 6.6 Hz, 1 H), 5.05–5.04 (m, 1 H), 5.00 (dd, J = 10.2, 1.6 Hz, 1 H), 2.75–2.71 (m, 2 H), 2.42–2.37 (m, 2 H) ppm. 13 C NMR (100 MHz, CDCl 3 ): δ = 142.0, 138.2, 128.6, 126.2, 125.9, 115.0, 35.7, 35.5 ppm.…”

Synthesis and characterization of a supported Pd complex on carbon nanofibers for the selective decarbonylation of stearic acid to 1-heptadecene: the importance of subnanometric Pd dispersion

“…This can be due to thermal degradation of the [Pd 2 IJAn) 2 Cl 2 ] complex or formation of off-cycle species that reduce the AnPd/CNF (DMF) catalyst activity. 62,63 In order to elucidate the catalytic activity of the Pd aggregates observed in the catalysts, the decarbonylation reaction was carried out at 180°C using a previously reported heterogeneous catalyst composed of 0.6 wt% Pd nanoparticles of around 2.5 nm supported on carboxylated CNF-COOH ( Fig. S6 †).…”