A catalytic michael/horner-wadsworth-emmons cascade reaction for enantioselective synthesis of thiochromenes

A catalytic enantioselective sulfa-Michael/Horner-Wadsworth-Emmons reaction cascade has been developed, taking advantage of phosphonate as an electrophilic activator and a traceless binding site. Using a chiral bifunctional urea derivative as the catalyst, a variety of aryl and heteroaryl substituted thiochromenes was obtained in excellent yield with a high level of enantioselectivity.

Catalytic Asymmetric Michael Addition/Cyclization Cascade Reaction of 3-Isothiocyanatooxindoles with Nitro Olefins

The first organocatalytic asymmetric reaction of 3-isothiocyanatooxindoles with nitro olefins has been developed by using a cinchonidine-derived bifunctional catalyst. The resulting products, highly functionalized 3,2-pyrrolidinyl-substituted spirooxindole derivatives, were obtained in high yields with good diastereo- and enantioselectivities (up to dr >20:1 and er = 96:4). This Michael addition/cyclization cascade reaction employs monosubstituted nitro olefins and complements the Zn-II-catalyzed variant, which is only applicable to disubstituted nitro olefins.

Poly(alkylene itaconate)s - an interesting class of polyesters with periodically located exo-chain double bonds susceptible to Michael addition

Itaconic acid is a bio-sourced dicarboxylic acid that carries a double bond; although several reports have dealt with the radical-initiated chain polymerization of dialkyl itaconates, only a few studies have utilized it as a di-acid monomer to prepare polyesters. In this study, we demonstrate that dibutyl itaconate can be melt-condensed with aliphatic diols to generate unsaturated polyesters; importantly, we show that the double bonds remain unaffected during the melt polymerization. A particularly useful attribute of these polyesters is that the exo-chain double bonds are conjugated to the ester carbonyl and, therefore, can serve as excellent Michael acceptors. A variety of organic thiols, such as alkane thiols, MPEG thiol, thioglycerol, derivatized cysteine etc., were shown to quantitatively Michael-add to the exo-chain double bonds and generate interesting functionalized polyesters. Similarly, organic amines, such as N-methyl-benzylamine, diallyl amine and proline, also add across the double bond; thus, these poly(alkylene itaconate)s could serve as potentially bio-benign polyesters that could be quantitatively transformed into a variety of interesting and potentially useful functionalized polymers.

Tandem aziridine ring opening-disulfide formation-reduction-Michael addition in one-pot mediated by tetrathiomolybdate

A detailed study of tetrathiomolybdate mediated tandem regio- and stereoselective ring opening of aziridine, disulfide formation, reduction of disulfide bond and Michael reaction in a one-pot operation is reported. This constitutes four reactions that take place in one-pot operation. In the reaction of BnEt3N](4)MoS4 with an aziridine derived from cyclohexene and in the absence of Michael acceptor intermediates sulfonamidodisulfide and sulfonamidothiol were isolated and fully characterized. It has also been shown that it is possible to carry out selective opening of the aziridine ring in the presence of an epoxide. By incorporating a suitable Michael acceptor as part of the substrate, intramolecular 1,4-addition could be performed, to achieve the synthesis of sulfur containing acyclic, cyclic amino acid ester derivatives and thia-bicyclo3.3.1]nonane derivatives in good yields. (C) 2015 Elsevier Ltd. All rights reserved.

Entrevista a Michael Eigen : el hálito de la fe

"El Dr. Michael Eigen es psicoterapeuta, senior member y analista didáctico de la National Psychological Association for Psychoanalysis. Ha publicado más de una veintena de libros. Es reconocido mundialmente por su voz innovadora, a la vez trascendente y encarnada, profundamente comprometida con las problemáticas actuales. Con 79 años, es profesor en el programa de posdoctorado de psicoterapia y psicoanálisis de la universidad de Nueva York. Supervisa y ejerce la clínica en un pequeño consultorio frente al Central Park, donde a su vez dicta seminarios sobre Bion, Winnicott y Lacan hace más de 35 años. Ha sido editor del Psychoanalitic Review y ha desempeñado cargos en diversas instituciones. Su última publicación, Faith, es una refinada amalgama entre la experiencia y la novedad, entre lo conceptual y lo poético..."

Aldehídos en reacciones de Michael enantioselectivas catalizadas por derivados del prolinol

426 p. : graf.

Proceedings of the 1998 Science Board Symposium on The Impacts of the 1997/98 El Niño Event on the North Pacific Ocean and Its Marginal Seas

Preface [pdf, 0.01 Mb] James J. O'Brien The big picture - The ENSO of 1997-98 [pdf, 0.01 Mb] James E. Overland, Nicholas A. Bond & Jennifer Miletta Adams Atmospheric anomalies in 1997: Links to ENSO? [pdf, 0.54 Mb] Vladimir I. Ponomarev, Olga Trusenkova, Serge Trousenkov, Dmitry Kaplunenko, Elena Ustinova & Antonina Polyakova The ENSO signal in the northwest Pacific [pdf, 0.47 Mb] Robert L. Smith, A. Huyer, P.M. Kosro & J.A. Barth Observations of El Niño off Oregon: July 1997 to present (October 1998) [pdf, 1.31 Mb] Patrica A. Wheeler & Jon Hill Biological effects of the 1997-1998 El Niño event off Oregon: Nutrient and chlorophyll distributions [pdf, 1.13 Mb] William T. Peterson Hydrography and zooplankton off the central Oregon coast during the 1997-1998 El Niño event [pdf, 0.26 Mb] William Crawford, Josef Cherniawsky, Michael Foreman & Peter Chandler El Niño sea level signal along the west coast of Canada [pdf, 1.25 Mb] Howard J. Freeland & Rick Thomson The El Niño signal along the west coast of Canada - temperature, salinity and velocity [pdf, 0.49 Mb] Frank A. Whitney, David L. Mackas, David W. Welch & Marie Robert Impact of the 1990s El Niños on nutrient supply and productivity of Gulf of Alaska waters [pdf, 0.06 Mb] Craig McNeil, David Farmer & Mark Trevorrow Dissolved gas measurements at Stn. P4 during the 97-98 El Niño [pdf, 0.13 Mb] Kristen L.D. Milligan, Colin D. Levings & Robert E. DeWreede Data compilation and preliminary time series analysis of abundance of a dominant intertidal kelp species in relation to the 1997/1998 El Niño event [pdf, 0.05 Mb] S.M. McKinnell, C.C. Wood, M. Lapointe, J.C. Woodey, K.E. Kostow, J. Nelson & K.D. Hyatt Reviewing the evidence that adult sockeye salmon strayed from the Fraser River and spawned in other rivers in 1997 [pdf,0.03 Mb] G.A. McFarlane & R.J. Beamish Sardines return to British Columbia waters [pdf, 0.34 Mb] Ken H. Morgan Impact of the 1997/98 El Niño on seabirds of the northeast Pacific [pdf, 0.06 Mb] Thomas C. Royer & Thomas Weingartner Coastal hydrographic responses in the northern Gulf of Alaska to the 1997-98 ENSO event [pdf, 0.76 Mb] John F. Piatt, Gary Drew, Thomas Van Pelt, Alisa Abookire, April Nielsen, Mike Shultz & Alexander Kitaysky Biological effects of the 1997/98 ENSO in Cook Inlet, Alaska [pdf, 0.22 Mb] H.J. Niebauer The 1997-98 El Niño in the Bering Sea as compared with previous ENSO events and the "regime shift" of the late 1970s [pdf, 0.10 Mb] A.S. Krovnin, G.P. Nanyushin, M.Yu. Kruzhalov, G.V. Khen, M.A. Bogdanov, E.I. Ustinova, V.V. Maslennikov, A.M. Orlov, B.N. Kotenev, V.V. Bulanov & G.P. Muriy The state of the Far East seas during the 1997/98 El Niño event [pdf, 0.15 Mb] Stacy Smith & Susan Henrichs Phytoplankton collected by a time-series sediment trap deployed in the southeast Bering Sea during 1997 [pdf, 0.21 Mb] Cynthia T. Tynan Redistributions of cetaceans in the southeast Bering Sea relative to anomalous oceanographic conditions during the 1997 El Niño [pdf, 0.02 Mb] Akihiko Yatsu, Junta Mori, Hiroyuki Tanaka, Tomowo Watanabe, Kazuya Nagasawa, Yikimasa Ishida, Toshimi Meguro, Yoshihiko Kamei & Yasunori Sakurai Stock abundance and size compositions of the neon flying squid in the central North Pacific Ocean during 1979-1998 [pdf, 0.11 Mb] O.B. Feschenko A new point of view concerning the El Niño mechanism [pdf, 0.01 Mb] Nathan Mantua 97/98 Ocean climate variability in the northeast Pacific: How much blame does El Niño deserve? [pdf, 0.01 Mb] Vadim P. Pavlychev Sharp changes of hydrometeorological conditions in the northwestern Pacific during the 1997/1998 El Niño event [pdf, 0.01 Mb] Jingyi Wang Predictability and forecast verification of El Niño events [pdf, 0.01 Mb] (Document contains 110 pages)

Preliminary guide to the identification of the early life history stages of Gerreid fishes of the Western Central Atlantic

The family Gerreidae contains four genera and 13 species that occur in the western central North Atlantic. Adult gerreids are small to medium size fishes that are abundant in coastal waters, bays, and estuaries in tropical and warm temperate regions and sometimes occur in freshwaters. They are generally associate~ with grassy or open bottoms, but not with reefs. Gerreids are silvery fishes, with deeply forked tails, and extremely protrusible mouth that points downward when protracted. They apparently feed on bottom-dwelling organisms and at least one species (Eucinostomus gula) shows a distinct transition, during the juvenile period, from a planktivore (exclusively copepods) to a carnivore that includes a diet of almost solely polychaetes (Carr & Adams, 1973; Robins and Ray, 1987; Murdy et al., 1997). (PDF contains 10 pages)

Hydrazides and hydrazones as versatile Michael-Donors for iminium-catalyzed conjugate addition reactions

396 : il., graf.

Activación de aldehídos a,b-insaturados mediante aminocatálisis en procesos enantioselectivos. Cicloadiciones (3+2) y reacciones en cascada Michael/Henry

During the research that it is summarized in the present memory, the activation of enals via iminium ion catalysis in different transformations has been studied. Firstly, a 1,3-dipolar cycloaddition between stable azomethine ylides and a,b-unsaturated aldehydes catalyzed by a chiral imidazolidinone derivative has been optimized. Employing this methodology we have synthesized a large range of densely substituted pyrroloisoquinolines and pyrrolophthalazines with good yields and high values of diastereo- and enantioselectivity. Moreover, a mechanistic study has been carried out based on DFT calculations and experimental data which have allowed us to propose that the (3+2) cycloaddition reaction follows a sequential Michael addition/Mannich cyclization pathway. The formation of the iminium ion as a result of the condensation between the a,b-unsaturated aldehyde and the catalyst plays an essential role, regarding both reactivity and stereoselectivity. On the other hand we have developed a methodology to carry out a cascade Michael/Henry reaction followed by a sequential dehydration. Starting from simple substrates (2-nitromethylacrilates and a,b-unsaturated aldehydes) and employing a prolinol-derivative catalyst a series of quiral nitrocyclohexadienes have been synthesized.

Holding mirrors up to Hamlet: what Franco Zeffirellis and Michael Almereydas filmic adaptations of the play tell us about it

Hamlet (1601), de William Shakespeare, é, desde o Fólio de 1623, circundada por um enorme e variado volume de leituras, que abrangem desde textos críticos e teóricos até as mais diversas adaptações teatrais e cinematográficas. Desde o final do século 19, o cinema vem adaptando peças de Shakespeare, fornecendo novos pontos de vista e sugestões para a encenação dessa obra ao levá-la inúmeras vezes para as telas. Dentre uma longa lista de adaptações fílmicas de Hamlet, o Hamlet mainstream de Franco Zeffirelli (1990) e o Hamlet 2000 (2000), filme independente de Michael Almereyda, compõem o corpus eleito para análise nesta dissertação. Dialogando com noções de críticos e teóricos que desenvolveram estudos sobre o conceito de adaptação, tais como André Bazin, Robert Stam e Linda Hutcheon, sugiro uma desierarquização entre a peça shakespeariana e os filmes logo, entre literatura/teatro e cinema. O objetivo final deste trabalho encontra-se na proposta de uma reflexão sobre esses filmes enquanto potenciais materiais críticos elucidativos para o estudo da peça, úteis na discussão de alguns de seus mais importantes temas e/ou questões

Seasonal Occurrence of the White Shark, Carcharodon carcharias, in Waters off the Florida West Coast, with Notes on its Life History

The white shark, Carcharodon carcharias, is considered rare in the Gulf of Mexico; however, recent longline captures coupled with historical landings information suggest that the species occurs seasonally (winter-spring) within this region. We examined a total of seven adult and juvenile white sharks (185-472 em total length) captured in waters off the west coast of Florida. Commercial longline fisheries were monitored for white sharks during all months (1981-94), but this species was captured only from January to April. All white sharks were captured in continental shelf waters from 37 to 222 km off the west coast of Florida when sea surface temperatures ranged from 18.7° to 21.6°C. Depths at capture locations ranged from 20 to 164 m. Fishing gear typically used in Gulf of Mexico offshore fisheries may not be effective at capturing this species, and the apparent rarity of white sharks in this area may be, in part, a function of gear bias.