Search

A constant current electrochemical approach for the synthesis of 1-aminoisoquinoline derivatives through the Ru(II)-catalyzed annulation of benzamidine hydrochlorides with alkynes is reported herein. This method produces good yields of naphthyridine-based compounds via Ru(II)-catalyzed C-H bond cleavage, leading to the formation of new C-C and C-N bonds in a one-pot manner. Notably, the synergy of electricity and Ru catalysis offers broad reaction compatibility, accommodating a wide range of substrates with diverse steric and electronic properties. Additionally, this method also eliminates the use of stoichiometric amounts of external chemical oxidants.

The monocarbonylation and dicarbonylation reactions are well-established reactions in carbonylation chemistry. This work reports unusual oxidative adjacent triple carbonylation of the tertiary amine towards oxomalonamide synthesis using a Pd catalyst. The protocol involves the use of inert tertiary amines as an active reservoir of secondary amines through sp 3 C-N bond activation using O 2 as an ideal oxidant.

Synthesis of alk-2-ynl-Weinreb amides via Pd-catalyzed oxidative carbonylation of terminal alkynes and N , O -dimethylhydroxylamine hydrochloride at room temperature under low CO/O 2 pressure is reported for the first time. This protocol offers tolerance of various functional groups under mild reaction conditions. The protocol incorporates aromatic- and aliphatic-substituted alkynes through a one-step oxidative carbonylative route toward desired alkynyl Weinreb amides, which are of considerable importance as valuable synthetic building blocks.

Dispersions of two immiscible liquids stabilized by solid particles are termed as Pickering emulsions. Stability of such emulsions is affected by various parameters such as amount of solid particle, method of emulsification, size, and shape of particles, etc. In this study, MgO samples prepared by different methods and characterized by XRD, FESEM, HRTEM, DLS, and CO 2 -TPD techniques were utilized for stabilizing o/w Pickering emulsions. The effect of particle shape on Pickering Interfacial Catalysis (PIC) for Knoevenagel condensation was investigated. It was found that in the case of rod and plate shaped particles, emulsion stability and catalytic activity were higher as compared to those obtained with other MgO samples prepared. The applicability of the MgO-PIC system is also successfully demonstrated for gram scale synthesis (85 % yield in 30 min). The MgO-PIC system was found to be reusable for at least five cycles without substantial loss in activity., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Inc.)

Enzymatic synthesis of flavours, fragrances and food additives compounds have great demand and market value. Benzyl butyrate is commercially important flavour and food additive compound having global use around 100 metric tons/year and widely used in various industrial sectors. However, industrial synthesis of food additive benzyl butyrate is carried out by conventional chemical process which demands for the green biobased sustainable synthetic process. The present work reports steapsin catalyzed synthesis of benzyl butyrate for the first time in supercritical carbon dioxide (Sc-CO 2 ) reaction medium. All reaction variables are optimized in details to obtain competent conversion of 99% in Sc-CO 2 reaction medium. The developed steapsin catalyzed synthesis in Sc-CO 2 medium offered almost four-fold higher conversion to benzyl butyrate than organic (conventional) solvent. The steapsin biocatalyst was effectually recycled up to five reaction cycles in Sc-CO 2 medium. Moreover, the developed steapsin catalyzed protocol in Sc-CO 2 medium was extended to synthesize different ten industrially significant flavour fragrance compounds that offers 99% conversion and three to five-folds higher conversion than organic medium. Thus, the present steapsin catalyzed protocol offered improved synthesis of various commercially significant flavour compounds in Sc-CO 2. medium., Competing Interests: Declaration of Competing Interest Author declare that, there is NO conflict of interest., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Development of heterogeneous catalysts with tunable activity and selectivity has posed a persistent challenge. This study addresses this challenge by fabricating a hybrid environment through the combination of mesoporous silica and N-rich melamine dendron via covalent grafting, allowing for controllable growth and encapsulation of Pd NPs. This catalyst presented an excellent catalytic activity for the oxidative carbonylative self-coupling of aryl boronic acids to afford symmetric biaryl ketones using N-formyl saccharin as a sustainable solid CO source and Cu as a co-catalyst., (© 2023 Wiley-VCH GmbH.)

A simple, cost-effective, and straightforward method for the synthesis of 2,3-disubstituted indole scaffolds has been developed. The present protocol involves copper-mediated tandem hydroamination followed by C-H annulation of unprotected anilines with a wide range of internal alkynes. In the presence of Cu(OAc) 2 ·H 2 O and trifluoroacetic acid (TFA), the reaction proceeds well to afford a variety of substituted indole derivatives in moderate to good yields. This process was found to be compatible with both primary and secondary anilines coupled with aromatic/aliphatic alkynes. High-purity copper nanoparticles can be recovered after the reaction, revealing the cost-effectiveness and environmentally benign feature of the current protocol.

Copper sulfate catalyzed an efficient, inexpensive, and environment-friendly protocol that has been developed for N -arylation of amines with 1,3-cyclohexadione-derived aryliodonium ylides in water as a green solvent. Aromatic primary amines substituted with electron-donating as well as electron-withdrawing groups on the aryl ring reacted smoothly with iodonium ylides to give the corresponding diarylamines with good to excellent yields. Also, secondary amines underwent N -arylation to deliver tertiary amines with moderate yields., (Copyright © 2023, Nabar et al.)

An efficient synthesis of tertiary amides from aryl boronic acids and inert tertiary amines through the oxidative carbonylation via C(sp 3 )-N bond activation is presented. This protocol significantly restricts the homocoupling biarylketone product. It involves the use of a homogeneous PdCl 2 /CuI catalyst and a heterogeneous Pd/C based catalyst, which promotes C(sp 3 )-N bond activation of tertiary amines with aryl boronic acids. This process represents a ligand-free, base-free, and recyclable catalyst along with an ideal oxidant like molecular oxygen.

Rapid environmental changes triggered by the increase in the concentration of heat-absorbing gases such as CO2 in the atmosphere have become a major cause of concern. One of the ways to counter this growing threat will be to efficiently convert atmospheric CO2 into value-added products via the development of efficient transition-metal-catalyzed processes. Conversion of CO2 into bulk products such as CH3OH and methane as well as its incorporation into commercial polyurethane synthesis has been achieved and reviewed extensively. However, the efficient transformation of CO2 into fine chemicals and value-added chemicals has many fold advantages. Recent years have seen a rapid rise in the number of metal-mediated protocols to achieve this goal of converting CO2 into fine chemicals. These are essential developments given the requirement of several commodities and fine chemicals in various industrial processes and the utilization of atmospheric CO2 will help provide a sustainable solution to the current environmental problems. Accordingly, we present here a comprehensive compilation of catalytic processes, involving CO2 as the C1 source for reacting with substrates such as alkanes, alkenes, alkynes, amines, acid chlorides, alcohols, allyl boronates, alkenyl triflates, and many others to provide easy access to a wide variety of useful molecules. Such a technology would certainly prove to be beneficial in solving the problems associated with the environmental accumulation of CO2.

This review summarizes current developments, novel synthetic routes for Ruthenium tethered chiral catalyst, and its derivatives along with its application in asymmetric synthesis. The review also covers derivatization in tethering unit, modification in N-monofunctionalized ligand as well as ligation of other ligand with Ru metal in chiral catalyst. Apparently, the effect of a modified tethered catalyst in the enantioselective synthesis of chiral products as well as in synthetic chemistry is also discussed in detail., (© 2021 Wiley Periodicals LLC.)

The present work deals with the synthesis of lab-made carboxymethyl cellulose (CMC) and chitosan (CHI) based co-polymer cross-linked with glutaraldehyde (GLU) which is used as immobilization matrix for the immobilization of Candida rugosa (CRL) lipase (CMC:CHI:GLU:CRL). This immobilized biocatalyst was subjected to characterization such as lipase-activity, kinetic-parameters, water-content, surface-texture, stability and half-life time etc. Effect of various ultrasound parameters (power, frequency, duty cycle, exposure time) on lipase activity is also tested which indicated that, developed biocatalyst has significant activity-stability and half-life-time in ultrasonicated medium. Further, this biocatalyst was applied to synthesize biomass-derived furfuryl derivative which offering excellent conversion of 99 % of bio-based furfuryl ester. The synthetic protocol is optimized in detail (with twelve reaction parameters) under ultrasonicated medium. Recyclability study offered 68 % conversion of the furfuryl ester after sixth reuse. Moreover, the developed protocol is well extended to synthesize various commercially important compounds. Besides this, we investigated thermodynamic parameters (ΔG*, ΔH*, ΔS*) which demonstrating more feasibility of biocatalytic synthesis in ultrasonicated medium than conventional medium. Finally, green metrics evaluation parameters (E-factor, carbon-efficiency and mass-intensity) are studied which indicating efficient synergetic role of immobilized CMC:CHI:GLU:CRL lipase biocatalysis and ultrasonication in green and sustainable synthesis., (Copyright © 2020 Elsevier Inc. All rights reserved.)

The present study aimed to analyze reaction kinetics and mechanism for the synthesis of propyl benzoate in solvent-free conditions. Lipase was immobilized on Hydroxypropyl methylcellulose (HPMC) and polyvinyl alcohol (PVA) polymer blend by entrapment method. Among different lipases immobilized on a support, Candida cylindracea (CCL) showed excellent activity. Systematic studies were done to optimize the reaction conditions. The activation energy was found to be 16.2 kcal/mol for immobilized CCL. Kinetic parameters were calculated, which depicted that propyl benzoate synthesized using immobilized CCL followed the ternary complex model in which propanol inhibits lipase activity at higher concentrations. Recyclability of the catalyst was checked up to four catalytic cycles and 40% retention of activity was observed up to the fourth cycle. Finally, the applicability of developed protocol to synthesize various alkyl benzoates was explored.

This study presents a first report on ruthenium-catalyzed asymmetric transfer hydrogenation (ATH) of levulinic acid (LA) to chiral γ-valerolactone (GVL). ATH of LA has been explored with Noyori's chiral catalyst (Ru-TsDPEN) in methanol solvent. Efficacy of ATH reaction of LA was investigated under different reactions conditions such as temperature, catalyst, and hydrogen donor concentration. The effect of various organic tertiary bases along with formic acid (FA) as a hydrogen donor was studied, and N -methylpiperidine with FA (1:1 molar ratio) was revealed as an efficient hydrogen donor for ATH of LA to GVL furnishing chiral GVL with complete conversion and 93% enantiomeric excess (ee). This operationally simple and mild ATH protocol was tested for practical applicability of ATH of LA obtained from biomass waste (rice husk and wheat straw) and furnished chiral GVL with 82% ee., Competing Interests: The authors declare no competing financial interest., (Copyright © 2019 American Chemical Society.)

This review represents nickel, cobalt and palladium catalyzed C-H activation of sp 3 carbon, with special emphasis on methyl C-H activation. The importance of directing group assistance and effect of ligand on β- or γ- C(sp 3 )-H activation is summarized in this review. The mechanistic study for Ni, Co and Pd catalyzed sp 3 C-H bond functionalization also discussed in detail., (© 2019 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Homogeneous catalysts often show high activity and selectivity towards the various chemical transformations. Most of the transition metal-based active catalysts are expensive, rare, and have strict regulations for their use in pharmaceutical products. Hence, there is a requirement to develop suitable technologies for the practical separation and recycling of metal complex catalysts along with the sustainability of the process. This review focuses on the recent techniques used for the catalyst separation, their recovery, and recyclability of the homogeneous form of catalysts based on their economic compatibility and industrial applications. Various homogeneous catalysts have been reviewed on the basis of their support or media, active centres and recyclability aspects of the catalysts. This review gives brief insights into the varied examples of different recycling techniques utilized in the past 6-7 years., (© 2019 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Herein, an efficient, atom economic and external oxidant free approach has been disclosed for the synthesis of isoquinolines. Azines were employed for annulation reactions with alkynes via sequential C-H/N-N bond activation using an air-stable cobalt catalyst. The method takes advantage of the incorporation of both the nitrogen atoms of azines into the desired isoquinoline products, offering the highest atom economy. In addition, the developed protocol works under external oxidant as well as silver salt free conditions. Furthermore, the established methodology features a relatively broad substrate scope with high product yields and scalability up to the gram level.

This work documents the first palladium pincer complex-catalyzed carbonylative Sonogashira (CS) and carbonylative Suzuki-Miyaura (CSM) cross-coupling. Compared to previous protocols, which employ hazardous and toxic solvents, the aminophosphine pincer complex {[C 6 H 3 -2,6-(NHP{piperidinyl} 2 ) 2 ]Pd(Cl)} ( III ) catalyzes both the cross-coupling reactions in propylene carbonate, an eco-friendly and sustainable polar aprotic solvent. Advantageously, employing III allows the CS cross-coupling to be carried out at a palladium loading of 10 -4 mol % and the CSM cross-coupling to be carried out at 10 -6 mol %, thus resulting in catalytic turnovers of 10 5 and 10 7 , respectively. Relative comparison of the pincer complex with conventional palladium precursors Pd(OAc) 2 and PdCl 2 (PPh 3 ) 2 shows the efficiency and robustness of the pincer complex in effecting higher catalytic activity at low palladium loadings., Competing Interests: The authors declare no competing financial interest.

Palladium nanoparticles (NPs) are decorated on the surface of an amine-functionalized graphene oxide (Pd@APGO) and characterized by using various analytical techniques. In this methodology, the surface of graphene oxide is modified using the amine functional groups which help stabilization and distribution of Pd NPs very well and increases the surface electron density of NPs by electron donating from amine groups. This developed catalyst shows a high catalytic activity toward the Suzuki coupling and carbonylative Suzuki-Miyaura coupling reactions at mild reaction conditions. The amine on the graphene oxide plays a very crucial role to stabilize and increase the electron density of Pd NPs and prevents the leaching of Pd metals. The Pd@APGO catalyst showed excellent catalytic activity (>90%) with a large range of substrates for both of the reactions and provides five recycle runs without the loss of its activity., Competing Interests: The authors declare no competing financial interest.

The present work reports covalent immobilization of steapsin lipase (SL) on Immobead-350 support matrix (IMB) to make a robust biocatalytic system to work under supercritical carbon dioxide condition (Sc-CO 2 ). The developed biocatalyst (IMB:SL) was characterized in details and utilized to convert waste cooking sunflower oil (WCSO) into value-added energy chemical (biodiesel) in Sc-CO 2 . All reaction process parameters were optimized in detail which offered 86.33% yield of biodiesel from WCSO. The developed Sc-CO 2 protocol is compared with the solvent-free conventional synthesis, which indicates almost twofold higher yield of biodiesel in Sc-CO 2 media as compared to solvent-free condition. To extend the scope, we have tested fresh and waste cooking oils (WCO) from various sources, offering 81-94% yield of biodiesel. The biocatalyst activity was investigated in various parameters of supercritical condition to know the biocatalyst stability in Sc-CO 2 . Besides this, IMB:SL biocatalyst was effectively reused up to five recycle.

Enantiopure intermediates are preferred for drug synthesis in pharmaceutical industry. Lipases are widely used for chiral resolution of optically active compounds based on kinetic resolution. In the kinetic resolution, two enantiomers react with different rates in presence of a chiral catalyst or reagent, resulting in obtaining one enantiomer of great excess compared to other. The enantiomeric ratio (E) is closely related to the free energy difference (ΔΔG) of the activated state of substrate enantiomers. Molecular dynamic (MD) simulations with umbrella sampling technique can be used for estimation of activation free energy change of enantiomers. In this work, lipase-catalyzed transesterification of racemic alcohols with single and double hydroxyl groups have been studied. The umbrella sampling studies have been carried out for Candida rugosa lipase and Burkholderia cepacia lipase in n-hexane. The distance between serine residue in the catalytic triad and the ligand has been considered as a reaction coordinate and various conformations have been selected for MD simulation. The E value has been estimated based on free energy change from umbrella sampling. The estimated E values are in good agreement with experimental data. The work highlights changes in lipase conformation in n-hexane, ligand-protein interaction as well as free energy curve as a function of the reaction coordinate., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The utility of a chiral Ru-prolinamide catalytic system has been demonstrated in one-pot synthesis of optically active β-triazolylethanol and β-hydroxy sulfone derivatives. The said methodology proceeds through asymmetric transfer hydrogenation of in situ formed ketones of the corresponding chiral products. Various chiral prolinamide ligands were screened, and ligand L6 with isopropyl groups substituted at the ortho position has shown excellent activity at 60 °C in aqueous medium producing up to 95% yield and 99.9% enantioselectivity., Competing Interests: The authors declare no competing financial interest.

This work reports a novel sustainable two-step method for the synthesis of ethylene glycol (EG) using syngas. In the first step, diethyl oxalate was selectively synthesized via oxidative double carbonylation of ethanol and carbon monoxide (CO) using a ligand-free, recyclable Pd/C catalyst. In the second step, the diethyl oxalate produced underwent subsequent hydrogenation using [2-(di- tert -butylphosphinomethyl)-6-(diethylaminomethyl)pyridine]ruthenium(II) chlorocarbonyl hydride to get EG and ethanol. Thus, the generated ethanol can be recycled back to the first step for double carbonylation. This method gives a sustainable route to manufacture EG using carbon monoxide and hydrogen., Competing Interests: The authors declare no competing financial interest.

A green and sustainable methodology for the synthesis of isoquinolines using Ru(ii)/PEG-400 as a homogeneous recyclable catalytic system has been demonstrated. N-Tosylhydrazone, a rarely explored directing group, has been successfully employed for an annulation type of reaction with alkynes via C-H/N-N activation. A short reaction time with a simple extraction procedure, a wide substrate scope with high yields of products, easily prepared substrates, biodegradable solvent, and scalability up to the gram level enhance the efficiency and sustainability of the proposed protocol. Further, the expensive ruthenium-based homogeneous catalytic system could be reused up to a fourth consecutive cycle without any loss in its activity.

Tethered ruthenium-TsDPEN complexes have been applied to the catalysis of the asymmetric transfer hydrogenation of a range of aryl/acetylenic ketones. The introduction of an ortho- substituent to the aryl ring of the substrate results in a reversal of the enantioselectivity, while the introduction of two o-fluoro substituents results in an improvement to the reduction enantioselectivity, as does the replacement of a phenyl ring on the alkyne with a trimethylsilyl group. These effects are rationalized as resulting from a change in the steric properties of the aryl ring and the electronic properties of the alkyne which, when matched in the reduction transition state, combine within a "window" of substrate/catalyst matching to generate products of high ee.

The present work reports an inverse electron demand Diels-Alder (iEDDA)-type reaction to synthesize 1,3,5-trizines from acetophenones and amidines. The use of molecular iodine in a catalytic amount facilitates the functionalization of the sp 3 C-H bond of acetophenones. This is a simple and efficient methodology for the synthesis of 1,3,5-triazines in good to excellent yields under transition-metal-free and peroxide-free conditions. The reaction is believed to take place via an in situ iodination-based oxidative elimination of formaldehyde. DFT calculations at the M062X/6-31+G(d,p) level were employed to investigate the reaction mechanism. Reaction barriers for the cycloaddition as well as a formaldehyde expulsion steps were computed, and a multistep mechanism starting with the nucleophilic attack by benzamidine on an in situ generated imine intermediate has been proposed. Both local and global reactivity descriptors were used to study the regioselectivity of the addition steps.

Kinetic resolution of rac-1,2-diols using the biocatalyst Burkholderia cepacia lipase (BCL) immobilized on a biodegradable binary blend support of hydroxypropyl methyl cellulose(HPMC)/polyvinyl alcohol (PVA) has been investigated. The immobilization technique improved enzyme activity significantly and it has excellent recyclability with good yield and enantiomeric excess values up to the studied range of nine cycles. At optimum reaction conditions, conversion of 45-50% with excellent enantiomeric excess (up to 99% ee) were obtained. It was observed that BCL shows enantio-preference to R form of primary hydroxyl group for acylation, whereas S form is preferred for diacetate formation. The resultant products were characterized with the help of different analytical techniques such as 1 H and 13 C NMR, chiral HPLC, IR and GC-MS. In order to understand the effect of solvent as well as various derivatives of substrates, combined molecular dynamics and docking simulations were carried out. Explanation related to experimentally observed enantio-selectivities have been provided based on transition state structures of acylated complexes., (Copyright © 2017 Elsevier B.V. All rights reserved.)

An electrochemical method for the synthesis of carboxylic as well as hindered esters from N-alkoxyamides has been reported. The electrochemical reaction proceeds through constant current electrolysis (CCE) by taking advantage of the dual role of n-Bu 4 NI (TBAI) as the redox catalyst as well as the supporting electrolyte. Besides providing mild reaction conditions, the present protocol is free from external oxidants and conducting salts, thereby generating nitrogen as the nonhazardous side product. Additionally, the developed procedure is highly advantageous due to its short reaction time, wide substrate scope, and gram-scale synthesis.

The present work deals with the designing of biocompatible hybrid blend of cellulosic copolymers made of hydroxypropyl methylcellulose (HMC) and chitosan (CHI) for immobilization of Rhizomucor miehei lipase (RML), in order to construct the robust biocatalytic system to synthesize industrially important dodecanoate compounds (fatty acid esters). The present biocatalyst HMC:CHI:RML was characterized in detail by various physical and biochemical methods and subsequently applied for the synthesis of fatty acid esters. The protocol was optimized in detail with kinetic parameters which provides excellent % conversion, and further we have synthesized fifteen industrially important compounds which have wide potential for commercial applications. The immobilized lipase HMC:CHI:RML offered four- to eightfold higher conversion and biocatalytic activity as compared to crude lipase. Besides this, recyclability study was also performed to assess economic and industrial viability.

This is the first report on the asymmetric transfer hydrogenation (ATH) of dibenzo[b,f][1,4]oxazepine compounds in the presence of an (R,R)-Ru-Ts-DPEN complex. The developed catalytic asymmetric protocol provides biologically active 11-substituted-10,11-dihydrodibenzo[b,f][1,4]oxazepines with excellent conversion (up to >99%) and high enantioselectivity (up to 93% ee) in water as an environmentally benign solvent.

This work reports tert-butyl nitrite (TBN) as a multitask reagent for (1) the controlled synthesis of N-nitrosoamide from N-alkyl amides, (2) hydrolysis of N-methoxyamides to carboxylic acids, (3) metal- and oxidant-free benzocoumarin synthesis from ortho-aryl-N-methoxyamides via N-H, C-N, and C-H bond activation, and (4) isocoumarin synthesis using Ru(II)/PEG as a recyclable catalytic system via ortho-C-H activation and TBN as an oxygen source. The sequential functional group interconversion of amide to acid has also been examined using IR spectroscopic analysis. Additionally, this methodology is highly advantageous due to short reaction time, gram scale synthesis, and broad substrate scope.

In the present work, we have investigated biochemical thermo-kinetic stability of lipases immobilized on a biocompatible polymeric material. Immobilization of lipase Candida rugosa (CRL) was carried out on biocompatible blend of poly vinyl alcohol (PVA) and chitosan (CHY) support via entrapment and glutardehyde (Glu) cross-linking method to produce PVA:CHY:CRL and PVA:CHY:Glu:CRL as robust biocatalyst. These immobilized lipases were characterized by various physico-biochemical characterization techniques. Later on, thermal and solvent stability of polymer immobilized lipase was determined in term of half-life time (t 0.5 ), D values, enthalpy (ΔH°), entropy (ΔS°), and free energy (ΔG°) of deactivation at different temperatures and in various solvents. The thermodynamic deactivation stability trend was found as: cross-linked lipase CRL > entrapped lipase CRL > free lipase CRL. Moreover, kinetic parameters, such as K m , V max, and catalytic efficiency, were also determined to understand the kinetic features. The polymer immobilized enzyme was reused to investigate the economic viability of the developed biocatalyst.

The present study reports an improved approach for the preparation of ethylene glycol (EG) by using carbon monoxide as C1 chemical by a two-step oxidative carbonylation and hydrogenation sequence. In the first step, oxamates are synthesized through oxidative cross double carbonylation of piperidine and ethanol by using Pd/C catalyst under phosphine ligand-free conditions and subsequently hydrogenated by Milstein's catalyst (carbonylhydrido[6-(di-t-butylphosphinomethylene)-2-(N,N-diethylaminomethyl)-1,6-dihydropyridine]ruthenium(II)). The presented stepwise oxamate-mediated coupling provides the basis for a new strategy for the synthesis of EG by selective upgrading of C1 chemicals., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A series of highly efficient, bifunctional ionic liquids containing a quaternary alkyl ammonium cation and an amine anion were prepared from choline and amino acids, respectively. Nine ILs were synthesized, characterized, and applied as organocatalysts for the chemical fixation of carbon dioxide to form cyclic carbonates and quinazoline-2,4(1 H,3 H)-diones. A binary mixture of an IL and a co-catalysts generates deep eutectic solvents (DESs) and accelerates the rate of the cycloaddition reaction at atmospheric pressure and low temperature (70 °C). The presence of the hydroxyl functional group of choline and the free amine group of the amino acids in the ILs has a synergistic effect on the activation of the epoxide and carbon dioxide towards the cycloaddition reactions. These ILs are biodegradable and are synthesized from easily available biorenewable sources. Additionally, this catalytic method demonstrates ultimate environmental benignity because of the mild metal- and solvent-free conditions as well as the recyclability of the catalyst and co-catalyst., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The utility of tethered Ru-TsDPEN catalyst has been demonstrated for the asymmetric transfer hydrogenation of rac-α-heteroaryl amino cycloalkanones to construct biologically important cis-β-heteroaryl amino cycloalkanols with two contiguous chiral centers via dynamic kinetic resolution. The stated (R,R)-Teth-TsDPEN-Ru-catalyzed transformation is carried out under mild conditions using formic acid/triethylamine as a hydrogen source with excellent diastereo- and enantioselectivities. Further, this methodology has been applied for the synthesis of an antileishmanial agent and chiral ionic liquid.

This work reports the synthesis of quinazolines from 2-aminobenzylamines with N-substituted benzylamines in the presence of molecular iodine. The developed methodology works smoothly under transition-metal free, additive free and solvent free conditions. The use of O 2 as a green oxidant makes it a greatly economical, green and sustainable protocol. Moreover, no aqueous work up is required thereby enhancing the efficiency. A series of quinazoline derivatives were synthesized successfully in good to excellent yields.

This work reports a simple, efficient and alternative synthetic route for the preparation of benzoxazoles via tandem cyclization of 2-halophenols with amidines. The developed methodology is free from ligands and uses inexpensive and easily available CuCl as a catalyst. This protocol avoids the use of any oxidant or inorganic acids. Various benzoxazole derivatives were synthesized in good to excellent yields. To the best of our knowledge, this is the first time that the synthesis of benzoxazoles from 2-halophenols with both aromatic and aliphatic amidines is reported. Owing to the simplicity of this protocol, the preparation of benzoxazoles could be achieved at a gram scale level.

In this report, the activity of N-heterocyclic olefins (NHOs) as a newly emerging class of organocatalyst is investigated for the chemical fixation of carbon dioxide through reactions with aziridines to form oxazolidinones and the N-formylation of amines with polymethylhydrosiloxane (PMHS) or 9-borabicyclo[3.3.1]nonane (9-BBN) as the reducing agent under mild conditions. The exocyclic carbon atoms of NHOs are highly nucleophilic owing to the electron-donating ability of the two nitrogen atoms. This high nucleophilicity of the NHOs activates CO2 molecules to form zwitterionic NHO-carboxylate (NHO-CO2 ) adducts, which are active in formylation reactions as well as the carboxylation of aziridines to oxazolidinones., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The nature of bonding interactions between the cation and the anion of an ionic liquid is at the heart of understanding ionic liquid properties. A particularly interesting case is a special class of ionic liquids known as protic ionic liquids. The extent of proton transfer in protic ionic liquids has been observed to vary according to the interacting species. Back proton transfer renders protic ionic liquids volatile and to be considered as inferior ionic liquids. We try to address this issue by employing modern ab initio valence bond theory calculations. The results indicate that the bonding in the cation and the anion of a prototypical ionic liquid, ethylammonium nitrate, is fundamentally different. It is neither characteristic of covalent/polar covalent bonding nor ionic bonding but rather charge shift bonding as a resonance hybrid of two competing ionic molecular electronic structure configurations. An investigation of other analogous protic ionic liquids reveals that this charge shift bonding seems to be a typical characteristic of protic ionic liquids while the ionic solid analogue compound ammonium nitrate has less charge shift bonding character as compared to protic ionic liquids. Further the extent of charge shift bonding character has been found to be congruent with the trends in many physicochemical properties such as melting point, conductivity, viscosity, and ionicity of the studied ionic liquids indicating that percentage charge shift character may serve as a key descriptor for large scale computational screening of ionic liquids with desired properties.

The first highly effective Pd/C-catalyzed oxidative N-dealkylation/carbonylation of various aliphatic as well as cyclic tertiary amines with alkynes has been described. The selective sp(3) C-N bond activation of tertiary amines at the less steric side using O2 as a sole oxidant and a plausible reaction pathway for the reaction are discussed. The general and operationally simple methodology provides an alternative for the synthesis of a wide range of alk-2-ynamide derivatives under mild conditions. The present protocol is ecofriendly and practical, and it shows significant recyclability.

This work reports palladium-catalyzed phenanthridinone synthesis using the coupling of aniline and amide by formation of C-C and C-N bonds in a one-pot fashion via dual C-H bond activation. It involves simultaneous cleavage of four bonds and the formation of two new bonds. The present protocol is ligand-free, takes place under mild reaction conditions, and is environmentally benign as nitrogen gas and water are the only side products. This transformation demonstrates a broad range of aniline and amide substrates with different functional groups and has been scaled up to gram level.

In this article, we present the progress made in the area of carbonylative C-H functionalization, with special emphasis on arenes and alkanes. The importance of directing group assistance and C-H functionalization using CO surrogates is also included. The budding development in the area of transition metal-catalyzed C(sp(3))-H activation makes us feel it necessary to file a summary on the past, as well as current, contributions and a prospective outlook on the transition metal-catalyzed carbonylative transformation of C-H bonds, which is the focus of this review., (© 2016 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

An environmentally-benign carbocatalyst based on amine-functionalized graphene oxide (AP-GO) was synthesized and characterized. This catalyst shows superior activity for the chemical fixation of CO2 into cyclic carbonates at the atmospheric pressure. The developed carbocatalyst exhibits superior activity owing to its large surface area with abundant hydrogen bonding donor (HBD) capability and the presence of well-defined amine functional groups. The presence of various HBD and amine functional groups on the graphene oxide (GO) surface yields a synergistic effect for the activation of starting materials. Additionally, this catalyst shows high catalytic activity to synthesize carbonates at 70 °C and at 1 MPa CO2 pressure. The developed AP-GO could be easily recovered and used repetitively in up to seven recycle runs with unchanged catalyst activity., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The present work deals with the kinetic modeling and docking study for the furfuryl acetate synthesis using immobilized Burkholderia cepacia (BCL) lipase. Initially various lipases were immobilized on hydroxypropyl methyl cellulose (HPMC) and poly vinyl alcohol (PVA) base hybrid polymer matrix. After screening of various immobilized biocatalysts, HPMC:PVA:BCL was found to be a robust biocatalyst. Various reaction conditions were optimized using response surface methodology (RSM) based on a four-factor-three-level Box-Behnken design. The optimal conditions were obtained at molar ratio of 1:2 of furfuryl alcohol to acyl donor, temperature 50°C with catalyst loading of 30mg in 3mL of non-aqueous media toluene. Under these conditions 99.98% yield was obtained in 3h. The Arrhenius plot showed that the activation energy for furfuryl acetate synthesis was 10.68kcal/mol. The kinetics of reaction was studied close to optimized conditions which obey order bi-bi model. Molecular docking study was carried out to understand the active site of BCL which is responsible for the reaction. It was observed that the reaction proceeds via acylation of the active serine of BCL and demonstrating strong hydrogen bond between the substrate and histidine site. The catalyst recyclability study was carried up to five cycles., (Copyright © 2015 Elsevier Inc. All rights reserved.)

This work reports oxidative N-dealkylation/carbonylation of tertiary amines to tertiary amides by using molecular oxygen as a sole oxidant using a Pd/C catalyst. This protocol is free from ligands, additives, bases, and cocatalysts. Different tertiary amines as well as aryl iodides have been examined for this transformation, providing desired products in good to excellent yield.

The present work reports the use of biocatalyst and ultrasound for greener synthesis of cinnamyl propionate. The lipase Pseudomonas cepacia was immobilized on a copolymer of hydroxypropyl methyl cellulose and polyvinyl alcohol. This biocatalyst was u sed for ultrasound-assisted synthesis of cinnamyl propionate with the detailed optimization of various reaction parameters. Besides this, protocol was extended to synthesize various industrially important propionate esters. In addition to this, different enzyme-kinetic parameters such as r max and K m(vinyl propionate), K m(cinnamyl alcohol) and K i(cinnamyl alcohol) were studied which presented ordered bi-bi mechanism with an inhibition by cinnamyl alcohol. The developed biocatalyst demonstrated enhancement in catalytic activity and recyclability up to five recycles. Moreover, the biocatalyst was tested to investigate the effects of sonication via various characterization techniques such as scanning electron microscopy, thermogravimetry, and water content analysis.

In the present study, we have synthesized biocompatible hybrid blend of cellulosic polymers of hydroxypropyl-methyl-cellulose (HPMC) and chitosan (CHY) for the immobilization of Candida rugosa lipase (CRL). The immobilized biocatalyst HPMC:CHY:CRL was subjected for characterization such as SEM, TGA, water content analysis, lipase activity, specific activity and protein content analysis. The kinetic parameter study (Rmax/Km) demonstrated improved biocatalytic activity of lipase after immobilization on carbohydrate co-polymers of HPMC:CHY. This biocatalyst was then employed to study practical biocatalytic applications for kinetic resolution which provided 50% conversion and >94% enantiomeric excess of substrate/product (ees/eep). The protocol demonstrated excellent recyclability upto five cycles. Finally, we studied influence of immobilization on cellulosic polymers for substrate, structure and reactivity for kinetic resolution. Hence, we investigated R0 (initial reaction rate), E-value (enantioselectivity) and Ea (activation energy). This study confirms that, lipase immobilized on carbohydrate polymers had 3-4 folds higher biocatalytic activity as compared to crude CRL., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

An efficient method for the synthesis of 1,3,5-triazines by NIS-catalyzed oxidative cyclization of alcohols with amidines has been developed. The reaction works smoothly under transition-metal free and phosphine-free conditions to afford a wide range of 1,3,5-triazine derivatives in moderate to good yields. The synthetic methodology was achieved via in situ oxidation of alcohols to aldehydes.

This work reports the carbonylative Suzuki-Miyaura coupling of aryl iodides catalyzed by palladacycles. More importantly, the palladacycles have been used to generate high turnover numbers (TON's) and turnover frequencies (TOF's). A range of aryl iodides can be coupled with arylboronic acids, generating TON's in the range of 10(6) to 10(7) and TOF's in the range of 10(5) to 10(6) h(-1). Comparison of the palladacycles with a conventional palladium source shows their superiority in generating high TON's and TOF's.

A visible-light-mediated procedure for the unprecedented trifluoromethylchlorosulfonylation of unactivated alkenes is presented. It uses [Cu(dap)2]Cl as catalyst, and contrasts with [Ru(bpy)3]Cl2, [Ir(ppy)2(dtbbpy)]PF6, or eosin Y that exclusively give rise to trifluoromethylchlorination of the same alkenes. It is assumed that [Cu(dap)2]Cl plays a dual role, that is, acting both as an electron transfer reagent as well as coordinating the reactants in the bond forming processes., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)