Ionic liquids (ILs) are considered as highly useful materials for potential diverse uses such as greener and more convenient alternatives to volatile organic solvents, reagents, additives, ligands and co-solvents. Thermal stability, negligible vapor pressure and high polarity with ionic environments have possibly conferred some unique physico-chemical properties and a wider electrochemical window on ILs. More importantly, these properties are tuneable, depending on variations in alkyl chains and counter-anions. On the other hand, various transition-metal-catalyzed cross-coupling reactions constitute an important backbone of contemporary organic synthesis. A vast number of C–C and C-heteroatom cross-coupling reactions are reported in the presence of ILs, often showing better performance. The influence of IL on the action of a given catalyst or on the course of a reaction can be relatively complex, and is not understood well enough to be able to draw succinct conclusions. However, there are a few reports in the literature that help understand the role of actual and active catalytic species stabilized in an IL environment. Stabilization, which can be either helpful or detrimental to catalysis depends on specific circumstances. This review article is aimed primarily at summarizing the various applications of ILs during the past decade, focusing as far as possible on the task-specific properties of ILs in transition-metal-catalyzed C–C and C-heteroatom cross-coupling reactions. Several successful achievements and noteworthy progress in this field of research leads to the sensible conclusion that future prospects in this field of research are not only bright but promise new horizons.
Organic Chemistry plays an important role in energy, information, materials, population, health, environment and implementation of defence plan. Organic chemists therefore, have the greatest responsibility to devise methods of carrying out organic syntheses, which will reduce or even eliminate the by-products and solve the problem of environmental pollution from the source. One of the methods to achieve this is using non-conventional energy sources, such as microwave, ultrasound, and photochemical chemistry, in conjugation with non-toxic solvents, which dramatically reduces energy waste and reaction time. Experiments synergising these alternate energy sources like microwave sonication, photosonication or microwave photochemistry, have gained high popularity as cost- effective green strategies. Pooling the advantages of alternate energy sources with biocatalysis is another novel avenue of sustainable synthesis. Organic electrosynthesis has also emerged as an environmentally benign technique for the construction of C-C and C-hetero bonds. Highlights of significant developments in these areas define the scope of the present discussion.
Background Whether initial treatment for Parkinson's disease should consist of levodopa, dopamine agonists, or monoamine oxidase type B inhibitors (MAOBI) is uncertain. We aimed to establish which of these three classes of drug, as initial treatment, provides the most effective long-term control of symptoms and best quality of life for people with early Parkinson's disease.Methods In this pragmatic, open-label randomised trial, patients newly diagnosed with Parkinson's disease were randomly assigned (by telephone call to a central office; 1:1:1) between levodopa-sparing therapy (dopamine agonists or MAOBI) and levodopa alone. Patients and investigators were not masked to group assignment. Primary outcomes were the mobility dimension on the 39-item patient-rated Parkinson's disease questionnaire (PDQ-39) quality-of-life scale (range 0-100 with six points defined as the minimally important difference) and cost-effectiveness. Analysis was intention to treat. This trial is registered, number ISRCTN69812316.Findings Between Nov 9,2000, and Dec 22,2009,1620 patients were assigned to study groups (528 to levodopa, 632 to dopamine agonist, 460 to MAOBI). With 3-year median follow-up, PDQ-39 mobility scores averaged 1.8 points (95% CI 0.5-3.0, p=0.005) better in patients randomly assigned to levodopa than those assigned to levodopa-sparing therapy, with no increase or attrition of benefit during 7 years' observation. PDQ-39 mobility scores were 1.4 points (95% CI 0.0-2.9, p=0.05) better in patients allocated MAOBI than in those allocated dopamine agonists. EQ-5D utility scores averaged 0.03 (95% CI 0.01-0.05; p=0.0002) better with levodopa than with levodopa-sparing therapy; rates of dementia (hazard ratio [HR] 0.81,95% CI 0.61-1.08, p=0.14), admissions to institutions (0.86,0.63-1.18; 13=0.4), and death (0.85, 0.69-1.06, p=0.17) were not significantly different, but the upper CIs precluded any substantial increase with levodopa compared with levodopa-sparing therapy. 179 (28%) of 632 patients allocated dopamine agonists and 104 (23%) of 460 patients allocated MAOBI discontinued allocated treatment because of sideeffects compared with 11 (2%) of 528 patients allocated levodopa (p<0.0001).Interpretation Very small but persistent benefits are shown for patient-rated mobility scores when treatment is initiated with levodopa compared with levodopa-sparing therapy. MAOBI as initial levodopa-sparing therapy was at least as effective as dopamine agonists.
AbstractReview: [yielding organic disulfanes; 111 refs.
Organic compounds possessing S-S bonds, often called disulfides or more specifically disulfanes, have been widely applied in various fields ranging from biochemistry to different industrially important polymers, used as synthetic intermediates in other fine chemicals such as catenanes, rotaxanes, micelles, and also in areas like peptidomimetics, self-assembled monolayers (SAMs) etc. Such versatile applications have steered the development of several new methods for the preparation of organic disulfides. The present review has attempted to comprehensively summarize recent advances in the process of S-S bond formation, highlighting plausible mechanistic considerations, scope and limitations.
The [3+2] cycloaddition reaction between an alkyne and nitrone in the presence of copper catalyst leading to the formation of β-lactam is known as the Kinugasa reaction. Over the years, the Kinugasa reaction has been established as a robust and versatile route for the synthesis of β-lactam derivatives in both cis and trans configuration. This review has focused on various approaches highlighting recent stereoselective syntheses along with plausible mechanisms and other salient features.
Diverse organic reactions have been explored using the basic surface of KF/alumina. This article has reviewed on assorted applications of KF/alumina in the synthesis of acyclic, carbocyclic and heterocyclic molecules with special focus on recent applications during 2005 to mid 2010. Examples of reactions under solvent-free dry conditions highlighting the greener context are also discussed.
Since the discovery of penicillin in 1929, beta-lactam antibiotics have been recognized as potentially chemotherapeutic drugs of incomparable effectiveness, conjugating a broad spectrum of activity with very low toxicity. The primary motif azetidin-2-one ring (beta-lactam) has been considered as specific pharmacophores and scaffolds. With the advent of combinatorial chemistry and automated parallel synthesis coupled with ample interests from the pharmaceutical industries, recent trends have been driven mostly by adopting solid phase techniques and polymer-supported synthesis of beta-lactams. The present survey will present an overview of the developments on the polymer-supported and solid phase techniques for the preparation of beta-lactam ring or beta-lactam containing antibiotics published over the last decade. Both unsubstituted and substitutions with different functional groups at various positions of beta-lactams have been synthesized using solid phase technology. However, Wang resin and application of Staudinger [2+2] cycloaddition reaction have remained hitherto the major choice. It may be expected that other solid phase approaches involving different resins would be developed in the coming years.
Combination of CuI and Catechol violet (CuI-CV) was employed as catalyst for the first time in the C–S coupling reaction of a wide variety of aromatic halides, such as aryl iodides, bromo pyridines, activated aryl chlorides, and vinyl iodide with thiols to afford the corresponding thioethers in good to excellent yields. Broad range of functional group tolerance present in both the coupling partners has been observed in this reaction protocol.
Polyionic Amberlite resin formate (ARF), derived from commercially available Amberlite resin chloride by simple rinsing with aqueous formic acid, could be soaked with palladium(0) from palladium salts, the formate counteranion being the reducing source. The resulting Amberlite resin formate supported with palladium(0), ARF-Pd, showed excellent catalytic activity in Heck, Suzuki-Miyaura, and Sonogashira couplings with a range of substrates. The catalyst may be recovered easily and quantitatively without leaching and recycled; it was tested for five runs without any significant loss of activity.
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A simple, chemoselective transfer hydrogenation of aryl aldehydes with the aid of Amberlite((R)) resin formate (ARF), a stable H-donor, in the presence of catalytic ruthenium trichloride is described. Aromatic aldehydes and 1,2-diketones are reduced efficiently and selectively, while aryl ketones remain unchanged. Several other potentially reducible groups attached to the aromatic moiety are unaffected.
Formation of aryl- or heteroaryl-nitrogen (or -oxygen) bonds under ligand and solvent-free conditions are highly selective to the presence of copper. While bromoarenes undergo C-N (or -O) coupling in stoichiometric presence of copper, heteroaryl bromides require only catalytic amounts of copper(l) salts depending on the position of bromo substituents. Such selectivity coupled with ligand and solvent-free protocols appear promising from the viewpoint of ecology and economy and are more attractive as compared to the existing protocols.
A new polyionic resin-bound tetraphenylborate has been prepared, which can serve as efficient phenylating agent in Pd-catalyzed Suzuki-Miyaura (SM) coupling with aryl halides in the absence of any base. The conditions are mild, operationally simple and the polyionic resin can be recharged and reused for several runs.