1,721,020 research outputs found
Al(Salen) metal complexes in stereoselective catalysis
No full textSalen ligands are a class of Schiff bases simply obtained through condensation of two molecules of a hydroxyl-substituted aryl aldehyde with an achiral or chiral diamine. The prototype salen, or N,N′-bis(salicylidene)ethylenediamine has a long history, as it was first reported in 1889, and immediately, some of its metal complexes were also described. Now, the salen ligands are a class of N,N,O,O tetradentate Schiff bases capable of coordinating many metal ions. The geometry and the stereogenic group inserted in the diamine backbone or aryl aldehyde backbone have been utilized in the past to efficiently transmit chiral information in a variety of different reactions. In this review we will summarize the important and recent achievements obtained in stereocontrolled reactions in which Al(salen) metal complexes are employed. Several other reviews devoted to the general applications and synthesis of chromium and other metal salens have already been published
Asymmetric Reactions Enabled by Cooperative Enantioselective Amino- and Lewis Acid Catalysis
Full text linkOrganocatalysis—the branch of catalysis featuring small organic molecules as the catalysts—has, in the last decade, become of central importance in the field of asymmetric catalysis, so much that it is now comparable to metal catalysis and biocatalysis. Organocatalysis is rationalized and classified by a number of so-called activation modes, based on the formation of a covalent or not-covalent intermediate between the organocatalyst and the organic substrate. Among all the organocatalytic activation modes, enamine and iminium catalysis are widely used for the practical preparation of valuable products and intermediates, both in academic and industrial contexts. In both cases, chiral amines are employed as catalysts. Enamine activation mode is generally employed in the reaction with electrophiles, while nucleophiles require the iminium activation mode. Commonly, in both modes, the reaction occurs through well-organized transitions states. A large variety of partners can react with enamines and iminium ions, due to their sufficient nucleophilicity and electrophilicity, respectively. However, despite the success, organocatalysis still suffers from narrow scopes and applications. Multicatalysis is a possible solution for these drawbacks because the two different catalysts can synergistically activate the substrates, with a simultaneous activation of the two different reaction partners. In particular, in this review we will summarize the reported processes featuring Lewis acid catalysis and organocatalytic activation modes synergically acting and not interfering with each other. We will focus our attention on the description of processes in which good results cannot be achieved independently by organocatalysis or Lewis acid catalysis. In these examples of cooperative dual catalysis, a number of new organic transformations have been developed. The review will focus on the possible strategies, the choice of the Lewis acid and the catalytic cycles involved in the effective reported combination. Additionally, some important key points regarding the rationale for the effective combinations will be also included. π-Activation of organic substrates by Lewis acids, via formation of electrophilic intermediates, and their reaction with enamines will be also discussed in this review
Going Beyond Counting First Authors in Author Co-citation Analysis
Full text linkThe present study examines one of the fundamental aspects of author co-citation analysis (ACA) - the way co-citation
counts are defined. Co-citation counting provides the data on which all subsequent statistical analyses and mappings
are based, and we compare ACA results based on two different types of co-citation counting - the traditional type that
only counts the first one among a cited work's authors on the one hand and a non-traditional type that takes into
account the first 5 authors of a cited work on the other hand. Results indicate that the picture produced through this non-traditional author co-citation counting contains more coherent author groups and is therefore considerably clearer. However, this picture represents fewer specialties in the research field being studied than that produced through the traditional first-author co-citation counting when the same number of top-ranked authors is selected and analyzed. Reasons for these effects are discussed
Variations on the Author
Full text link“Variations on the Author” discusses two of Eduardo Coutinho’s recent films (Um Dia na Vida, from 2010, and Últimas Conversas, posthumously released in 2015) and their contribution to the general question of documentary authorship. The director’s filmography is characterized by a consistent yet self-effacing form of authorial self-inscription: Coutinho often features as an interviewer that rather than express opinions propels discourses; an interviewer that is good at listening. This mode of self-inscription characterizes him as an author who is not expressive but who is nonetheless markedly present on the screen. In Um Dia na Vida, however, Coutinho is completely absent form the image, while Últimas Conversas, on the contrary, includes a confessional prologue that moves the director from the margins to the center of his films. This article examines the ways in which these works stand out in the filmography of a director who offers new insights into the notion of cinematic authorship
Appropriate Similarity Measures for Author Cocitation Analysis
Full text linkWe provide a number of new insights into the methodological discussion about author cocitation analysis. We first argue that the use of the Pearson correlation for measuring the similarity between authors’ cocitation profiles is not very satisfactory. We then discuss what kind of similarity measures may be used as an alternative to the Pearson correlation. We consider three similarity measures in particular. One is the well-known cosine. The other two similarity measures have not been used before in the bibliometric literature. Finally, we show by means of an example that our findings have a high practical relevance.information science;Pearson correlation;cosine;similarity measure;author cocitation analysis
Photoredox radical conjugate addition of dithiane-2-carboxylate promoted by an iridium(III) phenyl-tetrazole complex: a formal radical methylation of Michael acceptors
No full textA readily accessible iridium(III) phenyl-tetrazole complex ([Ir(ptrz)(2)(tBu-bpy)](+), 2; Hptrz = 2-methyl-5-phenyl-tetrazole; tBu-bpy = 4,4'-di-tert-butyl-2,2'-bipyridine) is shown to be a versatile catalyst for a new photocatalytic Michael reaction. Under light irradiation in the presence of 2, a dithiane 2-carboxylic acid, obtained by simple hydrolysis of a commercially available ethyl ester, generates a 1,3-dithiane radical capable of performing addition to a variety of Michael acceptors (e.g., unsaturated ketones, esters, amides and malonates). This broad scope reaction with high yields is a formal photoredox addition of the elusive methyl radical and the adducts obtained can be starting materials for a variety of functionalized products. The excited-state oxidation potential of catalyst 2 allows selective formation of radicals only from alpha-heterosubstituted carboxylates. Chemical modification of this metal complex can tune the electrochemical properties, opening a route to new highly selective catalytic photo-oxidation reactions
Aluminum(III) Salen Complexes as Active Photoredox Catalysts
Full text linkMetallosalen are privileged complexes that have found important applications in catalysis. In addition, their luminescent properties have also been studied and used for sensing and biological applications. Salen metal complexes can be efficient photosensitizers, but they can also participate to electron transfer processes. Indeed, we have found that commercially available [Al(Salen)Cl] is an efficient photoredox catalyst for the synergistic stereoselective reaction of alkyl aldehydes with different bromo ketones and malonates to give the corresponding enantioenriched α-alkylated derivatives. The reaction was performed in the presence of a MacMillan catalyst. [Al(Salen)Cl] is able to replace ruthenium complexes, showing that also aluminum complexes can be used in promoting photoredox catalytic reactions
Dispelling the Myths Behind First-author Citation Counts
Full text linkWe conducted a full-scale evaluative citation analysis study of scholars in the XML research field to explore just how different from each other author rankings resulting from different citation counting methods actually are, and to demonstrate the capability of emerging data and tools on the Web in supporting more realistic citation counting methods. Our results contest some common arguments for the continued
use of first-author citation counts in the evaluation of scholars, such as high correlations between author rankings by first-author citation counts and other citation
counting methods, and high costs of using more realistic citation counting methods that are not well-supported by the ISI databases. It is argued that increasingly available digital full text research papers make it possible for citation analysis studies to go beyond what the ISI databases have directly supported and to employ more
sophisticated methods
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