Enantioselective Organocatalytic α-Fluorination of Aldehydes

The first direct enantioselective catalytic α-fluorination of aldehydes has been accomplished. The use of enamine catalysis has provided a new organocatalytic strategy for the enantioselective fluorination of aldehydes to generate α-fluoro aldehydes, an important chiral synthon for medicinal agent synthesis. The use of imidazolidinone 1 as the asymmetric catalyst has been found to mediate the fluorination of a large variety of aldehyde substrates with N-fluorobenzenesulfonimide serving as the electrophilic source of fluorine. A diverse spectrum of aldehyde substrates can also be accommodated in this new organocatalytic transformation. While catalyst quantities of 20 mol % were generally employed in this study, successful halogenation can be accomplished using catalyst loadings as low as 2.5 mol %

The direct arylation of allylic sp3 C–H bonds via organic and photoredox catalysis

The direct functionalization of unactivated sp3 C–H bonds is still one of the most challenging problems facing synthetic organic chemists. The appeal of such transformations derives from their capacity to facilitate the construction of complex organic molecules via the coupling of simple and otherwise inert building blocks, without introducing extraneous functional groups. Despite notable recent efforts1, the establishment of general and mild strategies for the engagement of sp3 C–H bonds in C–C bond forming reactions has proved difficult. Within this context, the discovery of chemical transformations that are able to directly functionalize allylic methyl, methylene and methine carbons in a catalytic manner is a priority. Although protocols for direct oxidation and amination of allylic C–H bonds (that is, C–H bonds where an adjacent carbon is involved in a C = C bond) have become widely established2,3, the engagement of allylic substrates in C–C bond forming reactions has thus far required the use of pre-functionalized coupling partners4. In particular, the direct arylation of non-functionalized allylic systems would enable access to a series of known pharmacophores (molecular features responsible for a drug’s action), though a general solution to this long-standing challenge remains elusive. Here we report the use of both photoredox and organic catalysis to accomplish a mild, broadly effective direct allylic C–H arylation. This C–C bond forming reaction readily accommodates a broad range of alkene and electron-deficient arene reactants, and has been used in the direct arylation of benzylic C–H bonds

Prevalence of face recognition deficits in middle childhood

Approximately 2-2.5% of the adult population is believed to show severe difficulties with face recognition, in the absence of any neurological injury – a condition known as developmental prosopagnosia (DP). However, to date no research has attempted to estimate the prevalence of face recognition deficits in children, possibly because there are very few child-friendly, well-validated tests of face recognition. In the current study, we examined face and object recognition in a group of primary school children (aged 5-11 years), to establish whether our tests were suitable for children; and to provide an estimate of face recognition difficulties in children. In Experiment 1 (n = 184), children completed a pre-existing test of child face memory, the CFMT-K, and a bicycle test with the same format. In Experiment 2 (n = 413), children completed three-alternative forced choice matching tasks with faces and bicycles. All tests showed good psychometric properties. The face and bicycle tests were well-matched for difficulty and showed a similar developmental trajectory. Neither the memory nor matching tests were suitable to detect impairments in the youngest groups of children, but both tests appear suitable to screen for face recognition problems in middle childhood. In the current sample, 1.2-5.2% of children showed difficulties with face recognition; 1.2-4% showed face-specific difficulties – that is, poor face recognition with typical object recognition abilities. This is somewhat higher than previous adult estimates: it is possible that face matching tests overestimate the prevalence of face recognition difficulties in children; alternatively, some children may “outgrow” face recognition difficulties

Telephone conversation impairs sustained visual attention via a central bottleneck

Recent research has shown that holding telephone conversations disrupts one's driving ability. We asked whether this effect could be attributed to a visual attention impairment. In Experiment 1, participants conversed on a telephone or listened to a narrative while engaged in multiple object tracking (MOT), a task requiring sustained visual attention. We found that MOT was disrupted in the telephone conversation condition, relative to single-task MOT performance, but that listening to a narrative had no effect. In Experiment 2, we asked which component of conversation might be interfering with MOT performance. We replicated the conversation and single-task conditions of Experiment 1 and added two conditions in which participants heard a sequence of words over a telephone. In the shadowing condition, participants simply repeated each word in the sequence. In the generation condition, participants were asked to generate a new word based on each word in the sequence. Word generation interfered with MOT performance, but shadowing did not. The data indicate that telephone conversation disrupts attention at a central stage, the act of generating verbal stimuli, rather than at a peripheral stage, such as listening or speaking

Playing dice with mice: building experimental futures in Singapore

This is a postprint of an article published in New Genetics and Society, 2011, Vol. 30, Issue 4 pp. 433 – 441 © 2011 copyright Taylor & Francis. New Genetics and Society is available online at: http://www.tandfonline.com/loi/cngs20#.UqsI0tJdU24This short paper adds to debates on the unfolding spaces and logics of biotechnological development bought together in the 2009 special issue of New Genetics and Society on ‘Biopolitics in Asia’. Though an unlikely comparison between the development of the genomic sciences and the building of gambling casinos in the city state of Singapore, it reflects on the nature of political and technological investments in this South-East Asian city. It argues that Western expectations of a link between scientific practices, and civic epistemologies linked to democratic decision-making, are replaced by a rather different future orientation to scientific experimentation, economic investment and social development in Singapore

Analyzing false memories in children with associative lists specific for their age

Two experiments attempted to resolve previous contradictory findings concerning developmental trends in false memories within the Deese-Roediger-McDermott (DRM) paradigm by using an improved methodology-constructing age-appropriate associative lists. The research also extended the DRM paradigm to preschoolers. Experiment 1 (N = 320) included children in three age groups (preschoolers of 3-4 years, second-graders of 7-8 years, and preadolescents of 11-12 years) and adults, and Experiment 2 (N = 64) examined preschoolers and preadolescents. Age-appropriate lists increased false recall. Although preschoolers had fewer false memories than the other age groups, they showed considerable levels of false recall when tested with age-appropriate materials. Results were discussed in terms of fuzzy-trace, source-monitoring, and activation frameworks

On the convex central configurations of the symmetric (ℓ + 2)-body problem

For the 4-body problem there is the following conjecture: Given arbitrary positive masses, the planar 4-body problem has a unique convex central configuration for each ordering of the masses on its convex hull. Until now this conjecture has remained open. Our aim is to prove that this conjecture cannot be extended to the (ℓ + 2)-body problem with ℓ ⩾ 3. In particular, we prove that the symmetric (2n + 1)-body problem with masses m1 = … = m2n−1 = 1 and m2n = m2n+1 = m sufficiently small has at least two classes of convex central configuration when n = 2, five when n = 3, and four when n = 4. We conjecture that the (2n + 1)-body problem has at least n classes of convex central configurations for n > 4 and we give some numerical evidence that the conjecture can be true. We also prove that the symmetric (2n + 2)-body problem with masses m1 = … = m2n = 1 and m2n+1 = m2n+2 = m sufficiently small has at least three classes of convex central configuration when n = 3, two when n = 4, and three when n = 5. We also conjecture that the (2n + 2)-body problem has at least [(n +1)/2] classes of convex central configurations for n > 5 and we give some numerical evidences that the conjecture can be true

Enantioselective Organocatalysis Using SOMO Activation

The asymmetric α-addition of relatively nonpolar hydrocarbon substrates, such as allyl and aryl groups, to aldehydes and ketones remains a largely unsolved problem in organic synthesis, despite the wide potential utility of direct routes to such products. We reasoned that well-established chiral amine catalysis, which activates aldehydes toward electrophile addition by enamine formation, could be expanded to this important reaction class by applying a single-electron oxidant to create a transient radical species from the enamine. We demonstrated the concept of singly occupied molecular orbital (SOMO) activation with a highly selective α-allylation of aldehydes, and we here present preliminary results for enantioselective heteroarylations and cyclization/halogenation cascades