1,720,957 research outputs found
Enantioselective synthesis of epi-emetine analogues: Control of the facial selectivity in a three-component domino Knoevenagel-hetero-Diels-Alder reaction
No full textThe domino Knoevenagel-hetero-Diels-Alder reaction of the aldehyde rac-8, Meldrum's acid 2 and enol ether 3 leads to the cycloadduct rac-17 as the main product which in a second domino process was transformed into the benzoisoquinolizidine rac-18 by solvolysis, hydrogenolysis, condensation and hydrogenation; rac-18 was used as a substrate for the synthesis of the two diastereomeric epiemetine analogues 9 and 10 with > 96% ee (9) and 80% ee (10), respectively, by condensation with the phenylethylamine 23, Bischler-Napieralski reaction and "enantioselective" hydrogenation using the chiral catalyst (R,R)-26
Enantioselective synthesis of epi-emetine analogues: Control of the facial selectivity in a three-component domino Knoevenagel-hetero-Diels-Alder reaction
No full textThe domino Knoevenagel-hetero-Diels-Alder reaction of the aldehyde rac-8, Meldrum's acid 2 and enol ether 3 leads to the cycloadduct rac-17 as the main product which in a second domino process was transformed into the benzoisoquinolizidine rac-18 by solvolysis, hydrogenolysis, condensation and hydrogenation; rac-18 was used as a substrate for the synthesis of the two diastereomeric epiemetine analogues 9 and 10 with > 96% ee (9) and 80% ee (10), respectively, by condensation with the phenylethylamine 23, Bischler-Napieralski reaction and "enantioselective" hydrogenation using the chiral catalyst (R,R)-26
Domino reactions in the synthesis of heterocyclic natural products and analogs
No full textDomino reactions are defined as processes of two or more bond-forming reactions under identical conditions, in which the subsequent transformation takes place at the functionalities obtained in the former transformation. They allow the efficient synthesis of complex molecules from simple substrates in an ecologically and economically favorable way. A very powerful domino process is the domino Knoevenagel-hetero-Diels-Alder reaction, in which an aldehyde or an beta-ketoester is condensed with a 1,3-dicarbonyl compound or a heteroanalog to give a 1-oxa-1,3-butadiene, which can undergo an inter- or intramolecular hetero-Diels-Alder reaction with dienophiles such as enol ethers or alkenes. The products are dihydropyrans, which can be transformed in a variety of ways. Thus, an extension of the process is the synthesis of highly substituted pyrrolidines, piperidines, and azepanes using aminoaldehydes. The process has also been employed for the enantioselective total synthesis of a variety of alkaloids, such as indol- and ipecacuanha alkaloids. In another domino process, erythrina and homoerythrina alkaloids have been prepared from simple phenylethylamines and ketoesters
Enantioselective total syntheses of the Ipecacuanha alkaloid emetine, the Alangium alkaloid tubulosine and a novel benzoquinolizidine alkaloid by using a domino process
No full textThe first enantioselective syntheses of the Ipecacuanha alkaloid emetine (1) and the Alangium alkaloid tubulosine (2) is described employing a domino Knoevenagel/hetero-Diels-Alder reaction and an enantioselective catalytic transfer hydrogenation of imines as key steps. Thus, hydrogenation of the imine 15 with the catalyst (R,R)-16 gives the tetrahydroisoquinoline 14 with 95% ee which was transformed into the aldehyde (1S)-7. The three-component domino reaction of (1S)-7 with 6 and 8 led to 19, which in a second domino process was treated with K2CO3 in methanol followed by a hydrogenation to give the benzoquinolizidine 4 together with the diastereomers 22 and 23 in a overall yield of 66%. Further transformation of 4 with the amines 3 and 5 yielded enantiopure emetine (1) and tubulosine (2), respectively. In addition, starting from 19 the novel benzoquinolizidine alkaloid 34 was synthesised; this compound resembles the vallesiachotamine alkaloid dihydroantirhin 31, which has not been isolated so far but probably must also exist in nature
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
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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