Chiral transition-metal complexes as Brønsted-acid catalysts for the asymmetric Friedel-Crafts hydroxyalkylation of indoles.

The Friedel-Crafts reaction between 3,3,3-trifluoropyruvates and indoles is efficiently catalysed by the iridium complex [(η5-C 5Me5)Ir{(R)-Prophos}(H2O)][SbF 6]2 (1) with up to 84% ee. Experimental data and theoretical calculations support a mechanism involving the Brønsted-acid activation of the pyruvate carbonyl by the protons of the coordinated water molecule in 1. Water is not dissociated during the process and, therefore, the catalytic reaction occurs with no direct interaction between the substrates and the metal. This journal is © the Partner Organisations 2014.The authors acknowledge the Ministerio de Economía y Competitividad (MINECO, Grants CTQ2006-03030/BQU, CTQ2009-10303/BQU, CTQ2011-27033 and Consolider Ingenio 2010 CSD2006-003), Gobierno de Aragón (Grupo Consolidado: Catálisis Homogénea Enantioselectiva), Generalitat de Catalunya (2009SGR0259) and the ICIQ foundation for financial support. A. S. and R. R. acknowledge MINECO for predoctoral fellowships. S. D.-G. acknowledges MINECO for a “Torres Quevedo” contract.Peer Reviewe

Asymmetric 1,3-dipolar cycloaddition reactions between enals and nitrones catalysed by half-sandwich rhodium or iridium diphosphane complexes

The aqua complexes ¿(¿5-C5Me5)M¿PP*)¿H2O)]¿SbF6]2 (M = Rh, Ir; PP* = chiral diphosphane) have been tested as catalysts for the asymmetric 1,3-dipolar cycloaddition of nitrones to a,ß-unsaturated aldehydes. Quantitative conversions with very high regioselectivity, perfect endo selectivity and excellent enantioselectivity (up to 99% ee) were achieved. The stereochemical outcome was analyzed on the basis of the stereoelectronic properties of the intermediate enal complexes of the formula ¿(¿5-C5Me5)M¿PP*)¿enal)]¿SbF6]2

Effect of photoperiod and light intensity on larval rearing of bluefin tuna Thunnus thynnus

A couple of trials to test the effects of photoperiod and light intensity on growth and survival of Atlantic bluefin tuna larva were carried out. With regard to light intensity, no significant differences were found between 500, 1000 and 2000 luxes. With regards to photoperiod meanwhile long photoperiods lead to a greater growth, intermediate photoperiods (16hL:8hD and 12hL:12hD ) improve significantly survival rates.Research Project ATAME (CT M2011-29525-C04)

Heterobimetallic ruthenium–zinc complexes with bulky N-heterocyclic carbenes: syntheses, structures and reactivity

The ruthenium–zinc heterobimetallic complexes, [Ru(IPr)2(CO)ZnMe][BArF4] (7), [Ru(IBiox6)2(CO)(THF) ZnMe][BArF4] (12) and [Ru(IMes)’(PPh3)(CO)ZnMe] (15), have been prepared by reaction of ZnMe2 with the ruthenium N-heterocyclic carbene complexes [Ru(IPr)2(CO)H][BArF4] (1), [Ru(IBiox6)2(CO)(THF)H][BArF4] (11) and [Ru(IMes)(PPh3)(CO)HCl] respectively. 7 shows clean reactivity towards H2, yielding [Ru(IPr)2(CO) (¿2-H2)(H)2ZnMe][BArF4] (8), which undergoes loss of the coordinated dihydrogen ligand upon application of vacuum to form [Ru(IPr)2(CO)(H)2ZnMe][BArF4] (9). In contrast, addition of H2 to 12 gave only a mixture of products. The tetramethyl IBiox complex [Ru(IBioxMe4)2(CO)(THF)H][BArF4] (14) failed to give any isol- able Ru–Zn containing species upon reaction with ZnMe2. The cyclometallated NHC complex [Ru(IMes)’ (PPh3)(CO)ZnMe] (15) added H2 across the Ru–Zn bond both in solution and in the solid-state to afford [Ru(IMes)’(PPh3)(CO)(H)2ZnMe] (17), with retention of the cyclometallati

The effect of different short pulse feeding regimes on growth and survival of Atlantic bonito larvae Sarda sarda

One of the most easily manipulated variables in fish larval culture is the photoperiod. Long light photoperiod regimes are commonly used to enhance growth in commercial species. However, for species with a piscivorous larval period, as the Atlantic bonito (Sarda sarda), long time exposure to light could lead to a lower survival through aggressive behavior and cannibalism. One alternative could be modifications of the light and dark cycles during the photophase. These modifications can result in short pulse feeding regimes since bonito larvae fill up their stomach completely during light hours but do not feed in darkness. Little is known about how such intermittent feeding regimes affect growth and survival in fish. In this study, we tried different alternating and continuous light regimes during the culture of bonito larvae to identify the best regime that maximizes growth and survival.Fertilized eggs of Atlantic bonito were obtained from different spontaneous spawning events by a captive broodstock at the Spanish Institute of Oceanography (IEO) in Mazarrón. Bonito larvae 8 days post hatch (dph) were reared in 150 l tanks equipped with a lid that was used to cover and uncover the tanks to manipulate the hours of light and therefore pulse feeding regimes. Bonito larvae were always fed with yolk sac seabream larvae ad libitum. A total of three experiments were conducted. In all, a continuous dark period of 7.5hours was maintained from 24:00 to 7:30. All light regimes had a total of 9 light hours except for one that had 15hours of light (15L:9D). In the first experiment, light regimes provided alternating light and dark conditions of either 1.5, 3 or 4.5hours from 7:30 to 24:00). In the second experiment, the 3hours alternating light regime was compared to two continuous regimes of 15hours of light (15L:9D) and 9hours of light (9L:15D). These two experiments were conducted at the same temperature, 24.7±0.4°C. The third experiment was identical to the second experiment but at colder temperatures, 21.4±0.45°C. All regimes had 3 replicates. 10 larvae were sub-sampled 3 days after the experiments began and were ended after 6 days when all larvae were sampled. Due to slower growth, the third experiment ended after 9 days. The larvae were measured in standard length and individual dry weights were calculated. Larvae were counted in the tanks every 3 days to estimate survivorship. Final larval sizes in the alternating light regimes were larger in the 3hours than those obtained in the 1.5 and 4.5hours (first experiment, Fig. 1a, Tukey test p0.01). The 3hours alternating light regime yielded the largest larval sizes at the end of the experiment compared to the other alternating regimes. Final sizes at the 3hours regime were larger than those obtained under the 9L:15D continuous light regime at both temperatures. The time to satiation and the elapsed time to evacuate food totally from the gut in a similar species is about 3-4hours (Young and Davis, 1990). Our results suggest that a better strategy for bonito larvae growth is to fill their stomach more than once per day followed by a resting period when food is being digested. However, no effect was observed in terms of survival, possibly due to high abundance of larval prey. Changes in the light regime that result in pulse feeding can be a good strategy to increase growth in larval cultures when fitting well the evacuation and satiation rates

First results on ongrowing of hatchery reared Atlantic bluefin tuna, Thunnus thynnus, kept in sea cages

Bluefin tuna (ABFT) fingerlings born in captivity were raised during 15 months in sea cages. ABFT were fed with raw fish, and they grew during this period from 4 gr to 8 kg. Mortality rate was great, mainly during the first three months. This is the first experience of ongrowing ABFT born in captivity.EU (SELFDOTT), Caladeros del Mediterráneo, S.A. Instituto Español de Oceanografí

Hydrophosphination of unactivated alkenes and alkynes using iron(II):catalysis and mechanistic insight

The catalytic addition of phosphines to alkenes and alkynes is a very attractive process that offers access to phosphines in a 100% atom-economic reaction using readily available and inexpensive materials. The products are potentially useful ligands and organocatalysts. Herein, we report the first example of intramolecular hydrophosphination of a series of nonactivated phosphinoalkenes and phosphinoalkynes with a simple iron β-diketiminate complex. Kinetic studies suggest that this transformation is first-order with respect to both the phosphine and the catalyst. A mechanistic interpretation of the iron-catalyzed hydrophosphination is presented, supported by the experimental evidence collected

Reproducción del atún rojo Thunnus thynnus en jaulas flotantes obtención de puestas masivas mediante implantes hormonales

In the frame of the SELFDOTT project (From capture based to SELF-sustained aquaculture and Domestication Of bluefin tuna, Thunnus thynnus) captive-reared Atlantic bluefin tuna (Thunnus thynnus) (n=15, estimated body weight=90 Kg) maintained for 3 years in captivity in El Gorguel (Cartagena, Spain) were administered a gonadotrophin releasing hormone agonist (GnRHa) implant underwater, during the natural spawning period for this species in the Mediterranean Sea (June). Beginning 48-72 h later, massive spawnings occurred everyday for 17 days, with a daily maximum fecundity of 34 million eggs. Egg collection was accomplished by placing a special curtain around the perimeter of the cage and at 6 m allowed the floating eggs to be maintained within the cage and be collected at night and sunrise with 500 ìm mesh size nets from the surface of the water.Proyecto SELFDOTT. UE