Selective Metathesis of α-Olefins from Bio-Sourced Fischer–Tropsch Feeds

Abstract

The search for a low-cost process for the valorization of linear α-olefins combining high productivity and high selectivity is a longstanding goal for chemists. Herein, we report a soluble ruthenium olefin metathesis catalyst that performs the conversion of linear α-olefins to longer internal linear olefins with high selectivity (>99%) under neat conditions at low loadings (50 ppm) and without the need of expensive additives. This robust catalytic process allowed us to efficiently and selectively re-equilibrate the naphtha fraction (C5–C8) of a Fischer–Tropsch feed derived from non-petroleum resources to a higher-value product range (C9–C14), useful as detergent and plasticizer precursorsThis work was supported by the European Community through the seventh framework program (CP-FP 211468-2 EUMET, grant to M.R., L.F., and E.B.). M.M. thanks the CNRS, the ENSCR, Rennes Métropole, and the Région-Bretagne for their financial support. A.P. thanks the Spanish MINECO for project CTQ2014- 59832-JIN, and L.C. acknowledges funding from the King Abdullah University of Science and Technology (KAUST

Bleaching Earths as Powerful Additives for Ru‐Catalyzed Self‐Metathesis of Non‐Refined Methyl Oleate at Pilot Scale

“…(b), Scheme 1] with the highest turnover number (TON) of 440 000 reporteds of ar. [8] Nevertheless, the economical viability of industrial processes at multi-tons cale depends not only on the catalyst efficiency and selectivity, [9] but also on the quality of the involved raw materials. [8] Nevertheless, the economical viability of industrial processes at multi-tons cale depends not only on the catalyst efficiency and selectivity, [9] but also on the quality of the involved raw materials.…”

Azoliniums, Adducts, NHCs and Azomethine Ylides: Divergence in Wanzlick Equilibrium and Olefin Metathesis Catalyst Formation

“…High selectivity for primary metathesis products (PMPs) from self‐metathesis of α‐olefins at low catalyst loadings requires robust catalysts to minimize isomerization (IP) and secondary metathesis products . At 50 °C and a catalyst loading of 50 ppm both Ru10 and Ru3 achieve 76 % conversion of neat 1‐octene over 3 and 2 hours, respectively (Scheme , Figure ).…”

“…At 50 °C and a catalyst loading of 50 ppm both Ru10 and Ru3 achieve 76 % conversion of neat 1‐octene over 3 and 2 hours, respectively (Scheme , Figure ). However, Ru10 exhibits significantly superior selectivity in this specialized OM, producing 97 % of PMP compared to Ru3 , 80 % . At the same temperature and 10 ppm loading, Ru10 affords 62 % conversion and 95 % selectivity over 8 hours, equivalent to a TON of 29,403 and a TOF of 3,675.…”

In Silico Switch from Second- to First-Row Transition Metals in Olefin Metathesis: From Ru to Fe and from Rh to Co

“…This reaction consists of the reorganization of two carbon-carbon double bonds using a metal carbene complex as the catalyst, following Chauvin's [7,8] mechanism. The nature of the metal is fundamental, ruthenium and molybdenum being the leading metals for this research [9][10][11], with scarce studies on other metals, such as rhodium [12], osmium [13], and iron [14,15].…”