Addizioni organocatalitiche asimmetriche di 1,3-dicarbonili a orto-chinoni metidi. Un nuovo metodo per la sintesi di 3,4-diidrocumarine e 4h-cromeni otticamente attivi

Questa tesi descrive lo sviluppo di una nuova metodologia che prevede l’utilizzo degli orto-chinoni metidi (o-QMs) in reazioni organocatalitiche asimmetriche. A causa della loro elevata instabilità e reattività, gli o-QMs sono stati impiegati in trasformazioni di sintesi asimmetrica solo di recente. Il metodo sviluppato prevede l’utilizzo di catalizzatori bifunzionali in grado di promuovere la generazione in situ degli intermedi reattivi a partire dai rispettivi 2-solfonilalchil fenoli, tramite eliminazione di acido solfinico. L’utilizzo di condizioni blandamente basiche sia per generare gli o-QMs che per l’attivazione dei partner nucleofili, risulta innovativo e permette non solo di ovviare all’intrinseca instabilità di questi intermedi, ma anche di impiegarli efficacemente in reazioni organocatalitiche con una varietà di nucleofili, come, ad esempio, l’acido di Meldrum, il malononitrile e vari composti 1,3 dicarbonilici. Le reazioni catalitiche portano alla formazione di 3,4-diidrocumarine, 4H-cromeni e xantenoni enantioarricchiti. Alcuni di questi composti sono dei precursori sintetici di composti naturali o sintetici biologicamente attivi e per avvalorare questa metodologia sono state proposte le sintesi formali di tre composti di interesse biologico: la (R)-tolterodina (il principio attivo del farmaco antimuscarinico Detrol®), (S)-4-metossidalbergione (allergene della Dalbergia Nigra) and SB-209670 / SB-217242 (due potenti antagonisti dell’endotelina).

A Facile synthesis of 3-Methylene-4-aryl-1,3,4,5-tetrahydro-benzo[b][1,4] di-azepin-2-ones and 3-arylemethylene-4,5-dihydro-3H-benzo[b][1,4]diazepin-2-ylamines

A simple and convenient synthesis of 3-methylene-4-aryl-1,3,4,5-tetrahydro-benzo[b][1,4] diazepin-2-ones was accomplished by the SN2 nucleophilic substitution of the acetates of Baylis-Hillman adducts of acrylate with 1,2-phenylenediamines followed by base-mediated intramolecular cyclization. On the other hand similar substrates derived from the Baylis-Hillman adducts of acrylonitrile via Pinner’s reaction leads to 3-arylmethylene-4,5-dihydro-3H-benzo[b][1,4]diazepin-2-ylamines in good yields..

Conjoint use of Dibenzosilole and Indan-1,3-dione Functionalities to Prepare an Efficient Non-Fullerene Acceptor for Solution-Processable Bulk-Heterojunction Solar Cells

A solution-processable, non-fullerene electron acceptor, 2,2′-(((5,5-dioctyl-5 H-dibenzo[b,d]silole-3,7-diyl)bis(thiophene-5,2-diyl))bis(methanylylidene))bis(1 H-indene-1,3(2 H)-dione) (called N5) comprised of dibenzosilole and 1,3-indanedione building blocks was designed, synthesized, and fully characterized. N5 is highly soluble in various organic solvents, has high thermal stability, and has energy levels matching those of archetypal donor poly(3-hexylthiophene). Solution-processable, bulk-heterojunction solar cells afforded promising power conversion efficiency of 2.76 % when N5 was used as a non-fullerene electron acceptor along with the conventional donor polymer poly(3-hexylthiophene). As per our knowledge, the material reported herein is the first example in the literature where synchronous use of such building blocks is demonstrated in the design an efficient, non-fullerene acceptor.

Paciano II: the report of a conversation on whaling and science, 1-3 March 2008 (Paciano, Umbria)

In 2006 the UK-based charity, Global Ocean, with local support from the Third Millennium Foundation, convened a Conversation among specialists about the problems facing the conservation of whales. Called "A consultation on whaling", this gathering was held in the ancient village of Paciano, in Umbria near the border with Tuscany, 15 – 17 October 2006. There were 15 participants from 11 countries. Dr Kees Lankester served as moderator. The outcome was an Aide Memoire which served to guide the participants in the run-up to the 2007 meeting of the International Whaling Commission (IWC), held in Anchorage, Alaska, in June. One point of agreement was that a second consultation should be held in the months following the Anchorage meeting, involving some but not necessarily all of the participants in the first, but concentrating this time on scientific issues – especially those encountered in the Scientific Committee of the IWC –with particular attention to informing a wider public about those scientific activities in relation to the problems confronting the IWC and the views of scientists about them. This document is the report of that Conversation, referred to as Paciano II. The moderator was Dr Giuseppe Notarbartolo di Sciara and the Report was written by Kieran Mulvaney in consultation with all participants, and with reference to an Aide Memoire prepared by the Rapporteur, Dr Russell Leaper. The sponsor and organisers have agreed with the general sentiment expressed by participants in Paciano II that further such conversations should be held at roughly yearly intervals and they will try to satisfy that desire. Although these future gatherings would be concerned with the living ocean they would not necessarily be restricted in future to consideration of whales and whaling. Discussions are on-going for selection of a theme which is of both scientific interest and practical concern for conservation of marine life and management of the uses of ocean space. (Document has 18 pages)

Paciano II: a report of a conversation on whaling and science, 1-3 March 2008

In 2006 the UK-based charity, Global Ocean, with local support from the Third Millennium Foundation, convened a Conversation among specialists about the problems facing the conservation of whales. Called "A consultation on whaling", this gathering was held in the ancient village of Paciano, in Umbria near the border with Tuscany, 15 – 17 October 2006. There were 15 participants from 11 countries. Dr Kees Lankester served as moderator. The outcome was an Aide Memoire which served to guide the participants in the run-up to the 2007 meeting of the International Whaling Commission (IWC), held in Anchorage, Alaska, in June. One point of agreement was that a second consultation should be held in the months following the Anchorage meeting, involving some but not necessarily all of the participants in the first, but concentrating this time on scientific issues – especially those encountered in the Scientific Committee of the IWC –with particular attention to informing a wider public about those scientific activities in relation to the problems confronting the IWC and the views of scientists about them. This document is the report of that Conversation, referred to as Paciano II. The moderator was Dr Giuseppe Notarbartolo di Sciara and the Report was written by Kieran Mulvaney in consultation with all participants, and with reference to an Aide Memoire prepared by the Rapporteur, Dr Russell Leaper. The sponsor and organisers have agreed with the general sentiment expressed by participants in Paciano II that further such conversations should be held at roughly yearly intervals and they will try to satisfy that desire. Although these future gatherings would be concerned with the living ocean they would not necessarily be restricted in future to consideration of whales and whaling. Discussions are on-going for selection of a theme which is of both scientific interest and practical concern for conservation of marine life and management of the uses of ocean space. (19 page document)

Evaluation of the beta-glucanolytic enzyme complex of Trichoderma harzianum Rifai for the production of gluco-oligosaccharide fragments by enzymatic hydrolysis of 1,3;1,6-beta-D-glucans

Botryosphaeran, a new exopolysaccharide from the endophytic fungus Botryosphaeria rhodina MAMB-05, and algal laminarin were hydrolyzed by partially-fractionated enzymes of the beta-glucanolytic complex from Trichoderma harzianum Rifai. beta-Glucanase fractions (F-I and F-II) separated by gel permeation chromatography presented different modes of attack on botryosphaeran and laminarin. Botryosphaeran was hydrolyzed to the extent of 66% (F-I) and 98% (F-II) within 30 min, and its main hydrolysis products were gluco-oligosaccharides of DP >= 4, with lesser amounts of glucose, di- and tri-saccharides. The action of enzyme fractions I and II on laminarin resulted in 15% conversion to glucose, while the percentage of saccharification was radically different (70% for F-I and 25% for F-II). The different product arrays within the polysaccharide hydrolysates can be explained by the difference in the enzymes' specificities within each enzyme fraction, and the molecular structures of the polysaccharides and their complexity.

(1→6)- and (1→3)(1→6)-β-glucans from Lasiodiplodia theobromae MMBJ: structural characterization and pro-inflammatory activity

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Isoxazolidines and oxazines: preliminary studies for the synthesis of N,O-heterocyclic systems via an organocatalyzed 1,3-Dipolar Cycloaddiction and a tandem reaction mediated by TEMPO salts

This thesis is the result of the study of two reactions leading to the formation of important heterocyclic compounds of potential pharmaceutical interest. The first study concerns the reaction of (1,3)-dipolar cycloaddition between nitrones and activated olefins by hydrogen bond catalysis of thioureas derivatives leading to the formation of a five-membered cyclic adducts, an interesting and strategic synthetic intermediate, for the synthesis of benzoazepine. The second project wants to explore the direct oxidative C(sp3)-H α-alkylation of simple amides with subsequent addition of an olefin and cyclization in order to obtain the corresponding oxazine. Both reactions are still under development.

Regiocontrolled Synthesis of Pyrazole Derivatives Through 1,3-Dipolar Cycloaddition Reaction And Synthesis of Helicene-Thiourea based and Polymer Supported Soos's Catalyst for Asymmetric Synthesis

In first part we have developed a simple regiocontrolled protocol of 1,3-DC to get ring fused pyrazole derivatives. These pyrazole derivatives were synthesized using 1,3-DC between nitrile imine and various dipolarophiles such as alkynes, cyclic α,β-ketones, lactones, thiocatones and lactums. The reactions were found to be highly regiospecific. In second part we have discussed about helicene, its properties, synthesis and applications as asymmetric catalyst.Due to inherent chirality, herein we have made an attempt to synthesize the helicene-thiourea based catalyst for asymmetric catalysis. The synthesis involved formation of two key intermediates viz, bromo-phenanthrene 5 and a vinyl-naphthalene 10. The coupling of these two intermediates leads to formation of hexahelicene.

Kulṭur-geshikhṭe : Bd. 1-3

Enth.: 1. Di maṭeriele kulṭur. 2. Di gezelshafṭlikhe kulṭur. 3. Di gaysṭige kulṭur