Origins of the Regioselectivity in the Lutetium Triflate Catalyzed Ketalization of Acetone with Glycerol: A DFT Study

Pierpont, Aaron W.; Batista, Enrique R.; Martin, Richard L.; Chen, Weizhong; Kim, Jin‐Kyung; Hoyt, Caroline B.; Gordon, John C.; Michalczyk, Ryszard; Silks, Louis A.; Wu, Ruilian

doi:10.1021/cs5010932

Cited by 25 publications

(15 citation statements)

References 43 publications

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“…Also, the heterogeneous catalysts are divided into four categories of zeolite-, heteropoly acid-, metal-, and polymers-based catalysts. As it can clearly be seen, the highest catalytic activity (complete conversions) were observed from the rare-earth triflate catalysts (Pierpont et al, 2015 ), Ni-Zr/activated carbon catalyst (Khayoon and Hameed, 2013 ), (L)Ru (II)@SBA-15 (Lazar et al, 2018 ), Amberlyst-47 (Guemez et al, 2013 ), and [5%V] Si-ITQ-6 (Vieira et al, 2018 ). The detail of each reaction process and optimum conditions reported in Table 3 .…”

Section: Catalytic Acetalization Of Glycerolmentioning

confidence: 94%

A Review on the Catalytic Acetalization of Bio-renewable Glycerol to Fuel Additives

et al. 2018

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The last 20 years have seen an unprecedented breakthrough in the biodiesel industry worldwide leads to abundance of glycerol. Therefore, the economic utilization of glycerol to various value-added chemicals is vital for the sustainability of the biodiesel industry. One of the promising processes is acetalization of glycerol to acetals and ketals for applications as fuel additives. These products could be obtained by acid-catalyzed reaction of glycerol with aldehydes and ketones. Application of different supported heterogeneous catalysts such as zeolites, heteropoly acids, metal-based and acid-exchange resins have been evaluated comprehensively in this field. In this review, the glycerol acetalization has been reported, focusing on innovative and potential technologies for sustainable production of solketal. In addition, the impacts of various parameters such as application of different reactants, reaction temperature, water removal, utilization of crude-glycerol on catalytic activity in both batch and continuous processes are discussed. The outcomes of this research will therefore significantly improve the technology required in tomorrow's bio-refineries. This review provides spectacular opportunities for us to use such renewables and will consequently benefit the industry, environment and economy.

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Section: Catalytic Acetalization Of Glycerolmentioning

confidence: 94%

A Review on the Catalytic Acetalization of Bio-renewable Glycerol to Fuel Additives

et al. 2018

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“…36−40 Furthermore, although some mechanistic hypothesis have been proposed, 26,41 theoretical in-depth studies are very rare. 42…”

Section: Introductionmentioning

confidence: 99%

“…36−40 Furthermore, although some mechanistic hypothesis have been proposed, 26,41 theoretical in-depth studies are very rare. 42 Some of us have long been involved in the development of Lewis acid catalysts for the sustainable transformation of vegetable oils and derivatives. 43−47 Within this field we recently communicated 47 preliminary results about a set of homogenous catalysts based on iron(III), capable of promoting the synthesis of solketal (five-member ketal in Scheme 2, where R 1 = R 2 = Me).…”

Section: ■ Introductionmentioning

confidence: 99%

Iron(III) Complexes for Highly Efficient and Sustainable Ketalization of Glycerol: A Combined Experimental and Theoretical Study

et al. 2019

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The growing production of biodiesel as a promising alternative and renewable fuel led as the main problem the dramatic increase of its by-product: glycerol. Different strategies for glycerol derivatization have been reported so far, some more efficient or sustainable than others. Herein, we report a very promising and eco-friendly transformation of glycerol in nontoxic solvents and chemicals (i.e., solketal, ketals), proposing three new families of Fe(III) compounds capable of catalysing glycerol acetalization with unpublished turn over frequencies (TOFs), and adhering most of the principles of green chemistry. The comparison between the activity of complexes of formula [FeCl 3 ( 1-R )] ( 1-R = substituted pyridinimine), [FeCl( 2-R , R′ )] ( 2-R , R′ = substituted O , O ′-deprotonated salens) and their corresponding simple salts reveals that the former are extremely convenient because they are able to promote solketal formation with excellent TOFs, up to 10 5 h –1 . Satisfactory performances were shown with respect to the entire range of substrates, with results being competitive to those reported in the literature so far. Moreover, the experimental activity was supported by an accurate and complete ab initio study, which disclosed the fundamental role of iron(III) as Lewis acid in promoting the catalytic activity. The unprecedented high activity and the low loading of the catalyst, combined with the great availability and the good eco-toxicological profile of iron, foster future applications of this catalytic process for the sustainable transformation of an abundant by-product in a variety of chemicals.

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“…The acetalization of acetone in glycerol was tested by Pierpont et al. 88 because it is reusable and water‐friendly, and 100 % acetone glycerol was transformed into Solketal at room temperature.…”

Section: Catalyst Designmentioning

confidence: 99%

“…A variety of catalytic types was tested for glycerol acetalization with aldehydes/ketones: natural catalysts (aluminosilicates and silicates), supported catalysts (salt, oxides, acids, metals, impregnated catalysts), and catalysts derived from precipitations (salt and oxides). The rare earth triflates 88, the catalysts loaded by Ni, synthesized by Khayoon et al. 84, 85, and with natural resources, montmorillonite 75, with a glycerol conversion up to 100 %, produced the best conversions and highest yields.…”

Section: Catalyst Designmentioning

confidence: 99%

Glycerol Conversion to Solketal: Catalyst and Reactor Design, and Factors Affecting the Yield

et al. 2021

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A significant amount of glycerol has been generated by the epidemic increment in several biodiesel industries globally, which should be utilized for the biodiversity of biodiesel. The synthesis of Solketal‐acetone glycerol as a possible fuel additive is one of the most crucial glycerol recovery paths. State‐of‐the‐art reviews on batch and continuous processes to produce Solketal and possible reaction mechanisms are presented. The design of reactors and catalysts is taken into consideration and the factors influencing the yield of the Solketal process are discussed in detail. Finally, conclusions with future recommendations are reported. The utility of glycerol for acetals and ketals is of current importance for scientists seeking to find the best working conditions by testing the different catalysts, reactants, temperatures, and reactor designs.

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Origins of the Regioselectivity in the Lutetium Triflate Catalyzed Ketalization of Acetone with Glycerol: A DFT Study

Cited by 25 publications

References 43 publications

A Review on the Catalytic Acetalization of Bio-renewable Glycerol to Fuel Additives

A Review on the Catalytic Acetalization of Bio-renewable Glycerol to Fuel Additives

Iron(III) Complexes for Highly Efficient and Sustainable Ketalization of Glycerol: A Combined Experimental and Theoretical Study

Glycerol Conversion to Solketal: Catalyst and Reactor Design, and Factors Affecting the Yield

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