DESign of Sustainable One-Pot Chemoenzymatic Organic Transformations in Deep Eutectic Solvents for the Synthesis of 1,2- Disubstituted Aromatic Olefins
The self-assembly of styrene-type olefins into the corresponding stilbenes was conveniently performed in the Deep Eutectic Solvent (DES) mixture 1ChCl/2Gly under air and in the absence of hazardous organic co-solvents using a one-pot chemo-biocatalytic route. Here, an enzymatic decarboxylation of p-hydroxycinnamic acids sequentially followed by a ruthenium-catalyzed metathesis of olefins has been investigated in DES solvent. Moreover, and to extend the design of chemoenzymatic processes in DESs, we also coupled the aforementioned enzymatic decarboxylation reaction to now concomitant Pd-catalyzed Heck-type C-C coupling to produce biaryl derivatives under environmentally friendly reaction conditions.
The combination of metal- and biocatalysis is a challenging but forward-looking topic in synthetic chemistry. The unique selectivity of enzymes paired with the broad range of applications of chemical catalysts enables an undreamed-of number of novel processes. Herein, we describe the application of immobilized phenolic acid decarboxylase (PAD) for the decarboxylation of para-coumaric acid and subsequent Pd-catalyzed Heck cross-coupling with an aryl halide in a fully integrated two-step continuou...
Atom Transfer Radical Polymerisation (ATRP) is one of the most important techniques to synthesize well-defined polymers with predetermined molecular weight, designed microstructure and tailor-made functionalities. Although ATRP has been extensively studied in a variety of common Volatile Organic Solvents (VOCs) and water, there is significantly less work done using fashionable and environmentally friendly Deep Eutectic Solvents (DESs). Aiming to develop greener ATRP routes by allowing the recycl...
This work was supported by the University of Alicante (VIGROB-316) and the Spanish Ministerio de Economia, Industria y Competitividad (CTQ2015-66624-P, PGC2018-096616-B-100). BS thanks Generalitat Valenciana (ACIF/2017/211) for a fellowship.
Last. Robert Kourist(Graz University of Technology)H-Index: 23
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Phenolic acid decarboxylase from Bacillus subtilis (BsPAD) converts several p-hydroxycinnamic acid derivatives into the corresponding p-hydroxystyrenes, which are considered to be promising bio-based aromatic chemicals. Despite the enzyme’s high activity and stability, the low solubility of its substrates presents severe limitations for the establishment of industrial processes. Accordingly, deep eutectic solvents (DESs) have emerged as interesting alternatives to aqueous or organic solvents and...
Last. Eva Hevia(University of Strathclyde)H-Index: 39
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: Despite their ubiquitous presence in synthesis, the use of polar organolithium reagents under environmentally benign conditions constitutes one of the greatest challenges in sustainable chemistry. Their high reactivity imposes the use of severely restrictive protocols (e.g., moisture- and oxygen-free, toxic organic solvents, inert atmospheres, low temperatures, etc.). Making inroads towards meeting this challenge, a new air- and moisture-compatible organolithium-mediated methodology for the an...
Last. Cristina Prandi(UNITO: University of Turin)H-Index: 26
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Directed ortho metalation (DoM) or nucleophilic acyl substitution (SNAc) can be efficiently programmed on the same aromatic carboxylic acid amide, in a choline chloride-based eutectic mixture, by simply switching the nature of the organolithium reagent. Telescoped, one-pot ortho-lithiation/Suzuki–Miyaura cross-couplings have also been demonstrated for the first time in Deep Eutectic Solvents.
The green and versatile character of deep eutectic solvents (DES) has turned them into significant tools in the development of green and sustainable technologies. For this purpose, their use in polymeric applications has been growing and expanding to new areas of development. The present review aims to summarize the progress in the field of DES applied to polymer science and engineering. It comprises fundamentals studies involving DES and polymers, recent applications of DES in polymer synthesis...
#2Nnamdi Akporji(UCSB: University of California, Santa Barbara)H-Index: 3
Last. Bruce H. Lipshutz(UCSB: University of California, Santa Barbara)H-Index: 93
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Previous studies have shown that aqueous solutions of designer surfactants enable a wide variety of valuable transformations in synthetic organic chemistry. Since reactions take place within the inner hydrophobic cores of these tailor-made nanoreactors, and products made therein are in dynamic exchange between micelles through the water, opportunities exist to use enzymes to effect secondary processes. Herein we report that ketone-containing products, formed via initial transition metal-catalyze...
Deep Eutectic Systems (DESs) are obtained by combining Hydrogen Bond Acceptors (HBAs) and Hydrogen Bond Donors (HBDs) in specific molar ratios. Since their first appearance in the literature in 2003, they have shown a wide range of applications, ranging from the selective extraction of biomass or metals to medicine, as well as from pollution control systems to catalytic active solvents and co-solvents. The very peculiar physical properties of DESs, such as the elevated density and viscosity, red...
Ultrafast addition of highly-polar organometallic reagents (RMgX/RLi) into cyclic carbonates (derived from CO2 as sustainable C1 synthon) has been studied, for the first time, in 2-MeTHF as green reaction media or in the absence of external VOC solvents, at room temperature and in the presence of air/moisture (i.e., without using protecting atmosphere); reaction conditions that are generally forbidden in the field of these highly-reactive main group organometallic compounds. The correct selectio...
Owing to a growing awareness towards environmental impact, the search for “greener”, safer, and cost-effective solvents able to replace petroleum-derived solvents has never been greater today. In this context, the use of environmentally responsible solvents like water and the so-called Deep Eutectic Solvents (DESs), constructed from bio-based compounds, has recently experienced important growth in several fields of sciences. This short review highlights the key features of the chemistry of water...
Abstract Nowadays large quantities of volatile organic compounds (VOCs) are used, although they present serious disadvantages. Developing alternative reaction media capable of replacing VOCs is of the upmost relevance. Among the surrogates, deep eutectic solvents (DESs) have received particular attention. This revision gathers all the organocatalytic transformations carried out in DESs, benchmarking these protocols against the corresponding transformation operating in traditional VOC solvents.
An efficient and selective N-functionalization of amides is first reported via a CuI-catalyzed Goldberg-type C-N coupling reaction between aryl iodides and primary/secondary amides run either in Deep Eutectic Solvents (DESs) or water as sustainable reaction media, under mild and bench-type reaction conditions (absence of protecting atmosphere). Higher activities were observed in an aqueous medium, though the employment of DESs expanded and improved the scope of the reaction to include also aliph...
#2Hua Zhao(UNC: University of Northern Colorado)H-Index: 36
Last. Gary A. Baker(MU: University of Missouri)H-Index: 73
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Biomolecules have been thoroughly investigated in a multitude of solvents historically in order to accentuate or modulate their superlative properties in an array of applications. Ionic liquids have been extensively explored over the last two decades as potential replacements for traditional organic solvents, however, they are sometimes associated with a number of limitations primarily related to cost, convenience, accessibility, and/or sustainability. One potential solvent which is gaining cons...
Last. Sabah Karimi(University of Tabriz)H-Index: 3
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Abstract Cellulose-modified magnetite-graphene oxide nanocomposite was prepared via click reaction and utilized for immobilization of palladium (Pd) nanoparticles without using additional reducing agent. The abundant OH groups of cellulose provided the uniform dispersion and high stability of Pd nanoparticles, while magnetite-graphene oxide as a supporting material offered high specific surface area and easy magnetic separation. The as-prepared nanocomposite served as a heterogeneous catalyst fo...
The use of micellar conditions to enable one-pot reactions involving both transition metal and enzymatic catalysts is reported. Representative enzymatic transformations under micellar conditions are unaffected by the presence of non-ionic surfactants, including designer surfactants such as TPGS-750-M. Furthermore, the presence of enzymes has a negligible effect on transition metal catalysis under micellar conditions in water. Finally, three one-pot chemoenzymatic reactions in water are reported ...
Here we report a chemoenzymatic approach to synthesize 1-octene from carbohydrates via ethenolysis of rhamnolipids. Rhamnolipids synthesized by P. putida contain a double bond between carbon five and six, which is experimentally confirmed via olefin cross metathesis. Utilizing these lipids in the ethenolysis catalyzed by a Grubbs−Hoveyda-type catalyst selectively generates 1-octene and with good conversions. This study shows the potential of chemoenzymatic approaches to produce compounds for the...