%0 Journal Article %T Ruthenium-Catalyzed Hydroformylation of the Functional Unsaturated Fatty Nitrile 10-Undecenitrile %+ Institut des Sciences Chimiques de Rennes (ISCR) %+ Centre de recherche Rhône-Alpes (CRRA) %+ Arkema %A Le Goanvic, Lucas %A Couturier, Jean-Luc %A Dubois, Jean-Luc %A Carpentier, Jean-François %Z This work was supported by the French National Research Agency, ANR project MEMCHEM (14-CE06-0022-02) and Arkema Co. %< avec comité de lecture %@ 1381-1169 %J Journal of Molecular Catalysis A: Chemical %I Elsevier %V 417 %P 116-121 %8 2016 %D 2016 %R 10.1016/j.molcata.2016.02.030 %K 10-Undecenenitrile %K Biphephos %K Hydroformylation %K Isomerization %K Ruthenium %Z Chemical Sciences/Organic chemistryJournal articles %X The hydroformylation of 10-undecenitrile (1), a route towards polyamide-12, has been studied using Ru-diphosphite catalysts. The reactions proceeded effectively by in situ combination of chloro precursors such as RuCl2(PPh3)3 and RuCl2(DMSO)4 with Biphephos. High productivities (TON up to 15,000 mol(aldehyde).mol(Ru)−1) were achieved by carrying the reactions at low catalyst loading ([1]0/[Ru] = 20,000), at 120 °C in toluene or acetonitrile under 20 bars CO/H2 (1:1), with 20 equiv of Biphephos vs. Ru. Up to 75% chemoselectivity for the aldehydes and very high regioselectivities for the linear aldehyde (l/b = 99:1) were reached under such optimized conditions. Lower loadings of Biphephos (down to 2.5 equiv. vs. Ru) did not affect the chemo- and regioselectivities but the activity. The Ru-Biphephos combinations showed a non-optimized hydroformylation TOFHF of ca. 2–7 min−1, that is ca. 1–2 order of magnitude lower than that of analogous Rh-based systems (TOFHF = ca. 80 min−1). These Ru-Biphephos systems are, however, incapable, under the conditions suitable for selective hydroformylation, to promote isomerization of internal olefins, and hence to achieve a tandem isomerization-hydroformylation process %G English %2 https://univ-rennes.hal.science/hal-01290441/document %2 https://univ-rennes.hal.science/hal-01290441/file/Ruthenium-Catalyzed%20Hydroformylation%20of%20the%20Functional-%20accepted.pdf %L hal-01290441 %U https://univ-rennes.hal.science/hal-01290441 %~ UNIV-RENNES1 %~ CNRS %~ INSA-RENNES %~ ENSC-RENNES %~ ISCR %~ SCR_OMC2012 %~ ISCR-OMC %~ STATS-UR1 %~ UR1-SPM %~ INC-CNRS %~ UR1-UFR-SPM %~ UR1-HAL %~ UR1-SDLM %~ TEST-UNIV-RENNES %~ TEST-UR-CSS %~ UNIV-RENNES %~ INSA-GROUPE %~ ANR %~ UR1-MMS %~ TEST2-HALCNRS