Rhodium versus Iridium Catalysts in the Controlled Tandem Hydroformylation-Isomerization of Functionalized Unsaturated Fatty Substrates. - Archive ouverte HAL Access content directly
Journal Articles ChemCatChem Year : 2015

Rhodium versus Iridium Catalysts in the Controlled Tandem Hydroformylation-Isomerization of Functionalized Unsaturated Fatty Substrates.

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Abstract

The hydroformylation of 10-undecenitrile (1) and related unsatd. fatty substrates (H2C[n.63742]CH(CH2)7CH2R; R=CO2Me, CH2Br, CHO) has been studied with rhodium, iridium, ruthenium, and palladium biphephos catalysts. The reactions proceeded effectively with all four systems, with high selectivities for the linear aldehyde (ratio of linear/branched aldehydes=99:1). The biphephos-bis[chloro(cyclooctadiene)iridium] system showed a non-optimized hydroformylation turnover frequency (TOFHF) of 770 h-1 that was only approx. 5 times lower than that of the rhodium-based system (TOFHF=3320 h-1); the palladium and ruthenium biphephos systems were less active (TOFHF=210 and 310 h-1, resp.). Upon recycling, remarkable productivities were achieved in both cases (TON≈58 000 mol(1/1-int) mol(Ir)-1 and 250 000 mol(1/1-int) mol(Rh)-1, in which int=internal olefin). Competitive isomerization of terminal to internal olefins occurred with these catalysts. Iridium biphephos systems allowed slightly better control of the distribution of the internal isomers than the rhodium biphephos catalyst, with higher ratios of 9-/8-undecenitrile (1-int).

Dates and versions

hal-01153426 , version 1 (19-05-2015)

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Jérémy Ternel, Jean-Luc Couturier, Jean-Luc Dubois, Jean-François Carpentier. Rhodium versus Iridium Catalysts in the Controlled Tandem Hydroformylation-Isomerization of Functionalized Unsaturated Fatty Substrates.. ChemCatChem, 2015, 7 (3), pp.513--520. ⟨10.1002/cctc.201402783⟩. ⟨hal-01153426⟩
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