Selective hydroformylation of open-chain conjugated dienes promoted by mesitylene-solvated rhodium atoms to give β,γ unsaturated monoaldehydes

Bertozzi, Sergio; Campigli, Nedo; Vitulli, Giovanni; Lazzaroni, Raffaello; Salvadori, Piero

doi:10.1016/0022-328x(94)05107-m

Cited by 51 publications

(48 citation statements)

References 15 publications

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“…22 Beside products 6 and 7 we have observed little amounts of other regioisomers, which have been identified using mass spectra and quantified as "others". Similar results have also been observed by Bertozzi and co-workers, who observed, however, compound 7 only as a side product.…”

Section: Resultsmentioning

confidence: 95%

“…Fell reported on rhodium catalysed hydroformylation giving a broad mixture of several C 6 and C 7 aldehydes. 22 It is also possible to achieve enantioselective hydroformylation of piperylene using (R,S)-BINAPHOS as a ligand, however the ee remained low (20%). 21 A more detailed study aimed towards the regioselectivity of piperylene hydroformylation yielded up to 60% of branched saturated aldehydes as the major products.…”

Section: Introductionmentioning

confidence: 99%

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Hydroformylation of piperylene and efficient catalyst recycling in propylene carbonate

2015

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In contrast to monoolefins, diene hydroformylation is still a demanding task. Some dienes like butadiene and isoprene have been investigated more intensively, however, 1,3-pentadiene ( piperylene) has been rarely investigated. Here, we present a systematic investigation of the hydroformylation of piperylene, using Rh(CO) 2 acac/Xantphos as an active catalyst which can be easily recycled in the green solvent propylene carbonate. Under the chosen conditions aldehyde yields of up to 82% have been obtained, while catalyst recycling was possible for up to six runs.Scheme 1 Hydroformylation of a terminal olefin.

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Section: Resultsmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

Hydroformylation of piperylene and efficient catalyst recycling in propylene carbonate

2015

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“…The only reported hydroaminomethylations of conjugated 1,3‐dienes are isoprene and cyclopentadiene . Both reactions suffer from low regioselectivity of the hydroformylation, on the one hand, and low catalytic activity of rhodium if applied to 1,3‐dienes, on the other . The latter is owing to the formation of relatively stable η 3 ‐allyl–Rh complexes…”

Section: Methodsmentioning

confidence: 99%

Renewable Surfactants through the Hydroaminomethylation of Terpenes

et al. 2017

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A catalytic system was developed to enable the use of industrially available terpenes (e.g., β‐myrcene, β‐farnesene) in hydroaminomethylation to obtain renewable building blocks for surfactants in two steps. This homogeneously catalyzed tandem reaction includes both hydroformylation and enamine condensation steps, followed by hydrogenation. Under the optimized conditions, the Rh/1,2‐bis(diphenylphosphino)ethane catalytic system delivers products in high yields (70 %) after short reaction times (3 h) with unprecedentedly high turnover frequency (TOF) values for the hydroformylation of 1,3‐dienes of over 739 mol mol−1 h−1. This is the highest TOF reported to date for the hydroformylation of a 1,3‐diene. Furthermore, regioselectivities of 97 % and above were observed in the hydroformylation step, which is extraordinarily high for the conversion of 1,3‐dienes. The terpene‐derived amines obtained were further functionalized to quaternary ammonium compounds that were found to show surface activity quite similar to that of industrially available quaternary ammonium compounds. The hydroaminomethylation of terpenes achieves higher step efficiency than industrial means and makes use of an alternative, renewable feedstock to synthesize more environmentally friendly surfactants.

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“…However, by using 1,3‐dienes, such as butadiene, various very interesting products can be formed under typical hydroformylation reaction conditions. (E/Z)‐3‐pentenal and 4‐pentenal are attractive intermediates for the production of valuable C6 compounds such as adipic acid, hexamethylenediamine and 1,6‐hexanediol via the selective conversion of 1,6‐hexanedial (adipaldehyde) as a central intermediate (Figure ) …”

Section: C4 Moleculesmentioning

confidence: 99%

“…Many research groups investigated hydroformylation of butadiene experimentally. In recent decades, however, the selectivity for adipic aldehyde has been low, which has led to further research . The highest reported selectivities to adipaldehyde in butadiene hydroformylation so far is 50 % .…”

Section: C4 Moleculesmentioning

confidence: 99%

Homogeneously Catalyzed 1,3‐Diene Functionalization – A Success Story from Laboratory to Miniplant Scale

et al. 2018

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For many years, the efficient use of resources has been a major and permanent challenge for the chemical industry. The implementation of alternative resources such as renewables and carbon dioxide has been a subject of considerable discussion, but also the more efficient use of long known bulk chemicals is of great interest. Among them, 1,3‐dienes such as 1,3‐butadiene from the C4 cut of the naphtha cracker as well as isoprene, piperylene and cyclopentadiene from the corresponding C5 section are important substrates. These dienes are presently employed in various markets, with the greatest importance being in the production of polymers and copolymers. However, homogeneous transition metal catalysis has proven to be a versatile tool to functionalize these important 1,3‐dienes to low molecular weight fine chemicals by introducing, for example, nitrogen, oxygen or silicon. Hence, an upgraded use of the corresponding products as agrochemicals, pharmaceuticals, fragrances or special detergents is close at hand. The main approaches in the topic of homogeneous functionalization reactions of the industrially relevant 1,3‐dienes will be summarized and discussed within the present article. Besides that, novel applications including renewable 1,3‐dienes, for example β‐myrcene and β‐farnesene, as well as the application of CO2 in telomerization, will be critically discussed.

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Selective hydroformylation of open-chain conjugated dienes promoted by mesitylene-solvated rhodium atoms to give β,γ unsaturated monoaldehydes

Cited by 51 publications

References 15 publications

Hydroformylation of piperylene and efficient catalyst recycling in propylene carbonate

Hydroformylation of piperylene and efficient catalyst recycling in propylene carbonate

Renewable Surfactants through the Hydroaminomethylation of Terpenes

Homogeneously Catalyzed 1,3‐Diene Functionalization – A Success Story from Laboratory to Miniplant Scale

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