Hydroformylation of vegetable oils: More than 50 years of technical innovation, successful research, and development

Vanbésien, T.; Monflier, Éric; Hapiot, F.

doi:10.1002/ejlt.201500196

Cited by 47 publications

(34 citation statements)

References 52 publications

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“…On the other hand, the hydroformylation of long-chain alkenes (>10 C), with a C=C bond in a deep internal position (>5 C away), remains poorly documented. While the hydroformylation of this kind of substrate without specific regioselectivities targeted (i.e., via the hydroformylation of both internal and terminal C=C bonds) is quite common [17][18][19][20][21], the more challenging tandem isomerization-hydroformylation for the synthesis of terminal aldehydes remains less-studied. In 2005, Behr and coworkers performed the tandem isomerization-hydroformylation of methyl oleate with a Rh-Biphephos catalyst leading the synthesis of terminal aldehydes remains less-studied.…”

Section: Introductionmentioning

confidence: 99%

Rhodium-Biphephos-Catalyzed Tandem Isomerization–Hydroformylation of Oleonitrile

et al. 2018

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Tandem isomerization-hydroformylation of oleonitrile (an 18-carbon nitrile with a remote internal (9-)C=C bond) has been studied using Rh-bisphosphite catalyst systems, targeting formation of the linear aldehyde. The best compromise between regioselectivity (l/b = 58:42) and chemoselectivity (60%) was obtained at 120 • C and 10 bar CO/H 2 (1:1) with a catalyst based on Biphephos at a 0.5 mol % catalyst load and a low ligand excess (2 equiv. versus Rh). These values stand among the better reported ones for the tandem isomerization-hydroformylation of long chain olefins with a single-component catalyst system.

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Section: Introductionmentioning

confidence: 99%

Rhodium-Biphephos-Catalyzed Tandem Isomerization–Hydroformylation of Oleonitrile

et al. 2018

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“…In contrast, Boerner and co‐workers employed a phosphite ligand in the I‐HF of isomeric n ‐octenes, leading to better linear selectivity (up to 48 % n ‐nonanal) . Thus, a literature survey suggested that both (bis)phosphites and bisphosphine can catalyze isomerizing functionalization reactions of internal alkenes at elevated temperatures (120–140 °C) . Among the long‐chain plant oils, linear selective I‐HF of methyl oleate is found to be catalyzed by bisphosphite ligands of type L1 (Figure ) …”

Section: Resultsmentioning

confidence: 99%

Isomerizing Hydroformylation of Cashew Nut Shell Liquid

2017

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A small library of bisphosphorus ligands was evaluated in the rhodium‐catalyzed isomerizing hydroformylation (I‐HF) of cashew nut shell liquid (CNSL). The rhodium complex of 1,2‐bis((di‐tert‐butylphosphanyl)methyl)benzene (BDTBPMB; L4) outperformed the other bisphosphite and bisphosphine ligands and unveiled a moderate selectivity of 28 % and 50 % in the I‐HF of CNSL monoene and methoxy‐protected monoene, respectively. The resultant aldehyde 16‐(3‐methoxyphenyl)hexadecanal P1′ was isolated and its identity was fully established. Application of bis‐phosphine ligand L4 in the I‐HF of highly challenging CNSL cardanol (S3) and methoxy‐protected CNSL cardanol yielded a linear selectivity of 74 %, although with reduced conversion. To demonstrate the synthetic utility of our strategy, the obtained aldehyde (derived from S3) was subjected to hydrogenation and the resultant 3‐(16‐hydroxyhexadecyl) phenol (P8) was isolated in 89 % isolated yield. High‐pressure NMR investigation revealed selective formation of a bis‐equatorial BDTBPMB–rhodium complex, which might be responsible for the excellent linear selectivity.

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“…Most of the reactions on oleochemicals occur at the fatty acid carboxy group and they are comparatively few examples on the alkyl chain. However, the presence of double bond(s) in unsaturated fatty acid derivatives allows the installation of a range of organic functions including aldehyde, epoxide, diol, ketone and diketone, α‐hydroxyketone, carbonate, among others . More importantly, cleavage reactions—mainly using methyl oleate as the archetype—can give access to building‐blocks with higher added value, essentially for surfactants and polymer applications.…”

Section: Introductionmentioning

confidence: 99%

Robust Organocatalysts for the Cleavage of Vegetable Oil Derivatives to Aldehydes through Retrobenzoin Condensation

Bah

Deruer

et al. 2018

Chemistry A European J

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A series of thiazolium salts was prepared and tested for the cleavage of the α-hydroxyketone derived from methyl oleate. The robustness of these precatalysts was determined by dynamic thermogravimetric analyses (TGA). It has been shown that the stability of these species is mainly governed by the nature of the counter-anion and some of them were found to be stable until 350-400 °C. The α-hydroxyketone derived from methyl oleate was cleaved under reactive distillation conditions using optimized, thermally robust N-butylthiazolium triflate to give the cleavage product, namely, nonanal and methyl azelaaldehydate, with 85 and 70 % yields. A range of α-hydroxyketones derived from several fatty acids was cleaved to give the corresponding bio-based aldehydes with up to 98 % isolated yields. Finally, this protocol was successfully applied to a high-oleic sunflower oil derivative.

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Hydroformylation of vegetable oils: More than 50 years of technical innovation, successful research, and development

Abstract: International audienceno abstrac

Cited by 47 publications

References 52 publications

Rhodium-Biphephos-Catalyzed Tandem Isomerization–Hydroformylation of Oleonitrile

Rhodium-Biphephos-Catalyzed Tandem Isomerization–Hydroformylation of Oleonitrile

Isomerizing Hydroformylation of Cashew Nut Shell Liquid

Robust Organocatalysts for the Cleavage of Vegetable Oil Derivatives to Aldehydes through Retrobenzoin Condensation

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