Highly product-selective and scalable rare-earth metal-catalyzed Meinwald rearrangement of epoxy oleochemicals under solvent-free conditions

Shaikh, Rafik Rajjak; Khan, Rais Ahmad; Alsalme, Ali

doi:10.1016/j.jiec.2018.03.041

Cited by 7 publications

(4 citation statements)

References 50 publications

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“…Op>miza>on with methyl cis-9,10-epoxystearate. Given that the Ti-SiO2 epoxida>on catalyst is not acidic enough to efficiently promote the Meinwald rearrangement of the cis-9,10epoxystearate to a mixture of 9-oxo-and 10-oxostearates (Scheme 5), a variety of homogeneous Lewis as alterna>ves to the already described, 30,31 and heterogeneous Brønsted acid catalysts, including SAC-13 32 and other sulfonic solids, was tested with this purpose (Table 1). Regarding reac>on condi>ons, TFT was used as solvent in most of the reac>ons in order to check the possibility of carrying out the two-steps process in one-pot or tandem.…”

Section: Meinwald Rearrangement Of Fa;y Epoxidesmentioning

confidence: 99%

“…29 With respect to rearrangement of epoxystearate, not many examples have been described in the literature. Conven>onal Lewis acids, such as BF3, 17 and less common ones, such as Bi(OTf)3 30 and YCl3 31 , have been used for this purpose with high conversion and selec>vity. On the other hand, heterogeneous sulfonic solids have been shown to be efficient Brønsted catalysts for this reac>on.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of fatty ketoesters by tandem epoxidation–rearrangement with heterogeneous catalysis

Dorado

Gil

Mayoral

et al. 2020

Catal. Sci. Technol.

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Section: Meinwald Rearrangement Of Fa;y Epoxidesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis of fatty ketoesters by tandem epoxidation–rearrangement with heterogeneous catalysis

Dorado

Gil

Mayoral

et al. 2020

Catal. Sci. Technol.

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“…A synthetic example is the production of methyl 9(10)‐oxostearate from EMO via bismuth trifluoromethanesulfonate‐catalyzed Meinwald rearrangement at 30°C for 2 h. Methyl 9,10‐dioxostearate is accessible when the reaction temperature is increased to 90°C and dimethyl sulfoxide is added as an oxygen donor (Doll et al, 2013). Meinwald rearrangement of EMO was also accomplished with catalytic heterogenous sulfonic acid resins (Amberlyst 15 and Nafion SAC‐13) and yttrium trichloride (YCl 3 ) (Rios et al, 2012; Shaikh et al, 2018). Tandem epoxidation and rearrangement of methyl esters of elaidic, erucic, ricinoleic, linoleic, and oleic acids to the corresponding ketones was reported with titanium‐silica (Ti‐SiO 2 ) and SAC‐13, both with catalytic TBHP as the epoxidation reagent, in refluxing trifluorotoluene.…”

Section: Introductionmentioning

confidence: 99%

A review of fatty epoxide ring opening reactions: Chemistry, recent advances, and applications

Moser

Cermak

Doll

et al. 2022

J Americ Oil Chem Soc

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Fatty epoxides are produced from the corresponding alkenes by oxidation in the presence of peracids or other oxidants. The classic method is the Prilezhaev epoxidation in which peracids are generated by in situ oxidation of formic or acetic acids with hydrogen peroxide. Epoxidized vegetable oils and esters are used directly as biobased plasticizers and stabilizers for poly(vinyl chloride) or as important platform chemicals for the oleochemical industry. Nucleophilic attack at the oxirane moiety affords a variety of ring opened monomeric or polymeric products, which in many cases undergo further synthetic modification to yield finished products. The most common nucleophiles include water, alcohols, carboxylic acids, acid anhydrides, and amines, although numerous others can also lead to valuable functionalized fatty derivatives. This review summarizes the chemistry of fatty epoxide ring opening reactions as well as applications of the resultant products. Literature from the last 20 years will be emphasized, although older publications of particular significance will be included. Important applications include biobased lubricants as well as polyols for subsequent production of polyurethanes. In addition, ring-opening reactions hitherto unreported on fatty oxiranes will be suggested to facilitate further advancements in the chemistry and utility of fatty epoxides. Finally, interest in fatty epoxides and their consequent products will continue to grow due to the simplicity, efficiency, and versatility of oxirane formation and ring opening as well as the continued societal transition away from petroleum to a sustainable, circular, low-carbon, and biobased economy.

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“…The Meinwald rearrangement of renewable resources has also been investigated. For example, Alsalme et al [26] recently showed the complete and selective rearrangement of epoxidized methyl oleate to the corresponding ketone (100% yield) with 3 wt% of YCl 3 as catalyst. Not only fatty acids, but also epoxidized vegetable oils could be rearranged successfully [21].…”

Section: Introductionmentioning

confidence: 99%

Sustainable catalytic rearrangement of terpene-derived epoxides: towards bio-based biscarbonyl monomers

Löser

Rauthe

Meier

et al. 2020

Phil. Trans. R. Soc. A.

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Seeking a sustainable and selective approach for terpene modification, a catalyst deconvolution approach was applied to the Meinwald rearrangement of (+)-limonene oxide as a model substrate to yield dihydrocarvone. In order to identify the most suitable catalyst and reaction conditions, different Lewis acids were evaluated. Bismuth triflate proved to be the most active catalyst under mild reaction conditions, with a low catalyst loading (1 mol%) and a relatively short reaction time (3 h). The optimized reaction conditions were subsequently transferred to other terpene-based epoxides, yielding different bio-based biscarbonyl structures, which constitute interesting and valuable substances, e.g. for polymer synthesis or as fragrances. Monoepoxides derived from ( R )-(−)-carvone and (+)-dihydrocarvone rearranged to the desired products with high selectivities and yields. γ-Terpinene dioxide could be transformed in a double rearrangement to the respective biscarbonyl in moderate yields. A better result was achieved for limonene dioxide after further adjustment of the protocol to reach acceptable yields with a low catalyst loading of 0.1 mol% using 2-methyl tetrahydrofuran as a sustainable solvent. Compared to many procedures described in the literature, this procedure represents a step towards an increased sustainability in terpene modification by considering several principles of Green Chemistry, such as renewable resources, catalysis and mild reaction conditions for elementary chemical transformations. This article is part of a discussion meeting issue ‘Science to enable the circular economy’.

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Highly product-selective and scalable rare-earth metal-catalyzed Meinwald rearrangement of epoxy oleochemicals under solvent-free conditions

Cited by 7 publications

References 50 publications

Synthesis of fatty ketoesters by tandem epoxidation–rearrangement with heterogeneous catalysis

Synthesis of fatty ketoesters by tandem epoxidation–rearrangement with heterogeneous catalysis

A review of fatty epoxide ring opening reactions: Chemistry, recent advances, and applications

Sustainable catalytic rearrangement of terpene-derived epoxides: towards bio-based biscarbonyl monomers

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