Asymmetric Synthesis of a Potent CXCR7 Modulator Featuring a Hindered Tertiary ß-Amino Amide Stereocenter.

A practical and asymmetric synthesis of a small-molecule CXCR7 modulator featuring a highly functionalized and hindered tertiary ß-amino amide framework is reported. The cornerstone of this strategy relied on the intermediacy of a reactive aziridinium species, which, following regioselective ring opening with cyanide, furnished the desired chiral ß-tertiary amino nitrile for further elaboration. As a means of further highlighting this synthetic strategy, an expanded scope of hindered ß-amino amide synthesis is also presented.

Asymmetric synthesis of (+)-17-epi-methoxy-kauran-3-one through tandem oxidative polycyclization-pinacol process.

A synthesis of (+)-17-epi-methoxy-kauran-3-one, an O-methylated isomer of the natural diterpene 17-hydroxy-kauran-3-one, has been achieved. The strategy is based on a diastereoselective oxidative polycyclization-pinacol tandem process consisting of transforming a functionalized phenol into a compact and complex tetracycle, which represents the main core of kaurane family members. The synthesis also includes an enantioselective Yamamoto's allylation, a diastereoselective Ru-catalyzed hydrocyanation, a ring-closing metathesis and a reductive isomerization process as key steps. The structure of our synthetic substrate was determined through comparison with an O-methylated derivative of the natural compound.

Asymmetric synthesis of the main core of kaurane family members triggered by an oxidative polycyclization-pinacol tandem process.

Polycyclization processes represent expeditious routes used in both nature and the laboratory to produce complex polycyclic molecules. A new stereoselective oxidative variant of such a polycyclization has been developed in which the cascade is triggered by a phenol dearomatization and is concluded by a pinacol transposition. This unprecedented avenue combines the synthetic power of a polycyclization and a transposition in tandem and enables the rapid formation of the tetracyclic main core of kaurane diterpenes containing several asymmetric and quaternary carbon centers in a single step from a simple phenol derivative.

New variations of intrahemispheric and interhemispheric processing indexed by the dimond paradigm.

We report 2 experiments designed to demonstrate that unilateral tachistoscopic stimulation would yield a response time (RT) advantage over bilateral stimulation in a simple experiment, whereas the opposite pattern would occur in a complex version of the same task, as predicted by the intrahemispheric resource limitation model of Banich and colleagues. Experiment 1 was a go/no-go task in which participants had to press a key when two shapes (circles or squares) were identical on the computer screen. A unilateral field advantage was obtained that was accentuated in several task conditions that yielded overall longer RTs, mostly in the bilateral condition. Experiment 2 was similar but required a more complex judgment: The go trials were to 2 stimuli identical on 1 dimension (shape or color) but not both or neither. The RTs were significantly and substantially longer than in Experiment 1 and exhibited a nonsignificant bilateral field advantage, which differed significantly from the unilateral field advantage obtained in Experiment 1. These results support the intrahemispheric resource limitation model of Banich and colleagues. However, several within-experiment effects are in direct opposition to this model and are best explained as limitations of commissural relay of perceptual information.

A stereoselective oxidative polycyclization process mediated by a hypervalent iodine reagent.

Activation of phenol derivatives with a hypervalent iodine reagent promotes the formation of bicyclic and tricyclic products via a cationic cyclization process. The method allows efficient one-step syntheses of scaffolds present in several natural products and occurs with total stereocontrol, governed by 1,3 allylic strain interactions and by the configuration of the side chain double bonds.

A choice reaction time index of callosal anatomical homotopy.

Tachistoscopically presented bilateral stimulus pairs not parallel to the meridian produced significantly longer RTs on a task requiring discrimination of shapes (Go/no-Go) than pairs emplaced symmetrically on each side of the meridian in Desjardins and Braun [Desjardins, S., & Braun, C. M. J. (2006). Homotopy and heterotopy and the bilateral field advantage in the Dimond paradigm. Acta Psychologica, 121, 125-136]. This was explained by the fact that there are more homotopic than heterotopic fibers in the corpus callosum. However: (1) different parts of the visual field were not equiprobably stimulated, possibly causing subtle biases, (2) the predicted cost of vertical asymmetry was tested only with bilateral stimuli, and (3) interstimulus distance was at the outer limit of callosal midline fusion (10.6 degrees ). Here, a tachistoscopic experiment with 24 normal participants replicated the between-field vertical symmetry advantage [Desjardins, S., & Braun, C. M. J. (2006). Homotopy and heterotopy and the bilateral field advantage in the Dimond paradigm. Acta Psychologica, 121,125-136.], but without irrelevant stimulation conditions and with more proximal stimuli. In addition, a significant specific cost of vertical asymmetry of 7ms was found for between-field integration over within-field integration. As far as we know, this is the first demonstration of an effect of callosal anatomical homotopy with reaction time.

Age-related differences in timing with breaks.

Two groups of participants differing in age were compared on a time production task during which timing was temporarily interrupted. Produced intervals lengthened with increasing delay before the break occurrence, and the effect was more pronounced in older than in younger adults. A reaction time response to the signal beginning the break period was required also. Older participants responded more slowly to this signal, but they benefited to a greater extent from a lengthening of the time preceding its presentation. These results suggest that performance of older participants is affected by attention sharing and preparation involved in timing with breaks.

Homotopy and heterotopy and the bilateral field advantage in the Dimond paradigm.

Pairs of homotopic and heterotopic visual bilateral stimuli and pairs of unilateral visual stimuli were presented to 12 normal right-handed university students requiring a key press if they were of the same form. As predicted from the known histology of the corpus callosum (massive preponderance of homotopic fibers), homotopic presentations yielded significantly faster reaction times than heterotopic stimulations. Bilateral pairs of stimuli were also advantaged in comparison with unilateral trials, replicating Sereno and Kosslyn [Sereno, A. B., & Kosslyn, S. M. (1991). Discrimination within and between hemifields: a new constraint on theories of attention. Neuropsychologia, 29, 659-675]. Moreover, certain attentional processes have never been investigated in the Dimond paradigm and this study provides evidence to the effect that discriminative reaction times to stimulus pairs are strongly influenced by their proximity to the fixation point. In similar previous experiments, the homotopy/heterotopy observation and the bilateral field advantage may have been distorted by that particular confound, as well as several others.