Synthesis, structural characterization, and chiroptical properties of planarly and axially chiral boranils

International audience2-Amino[2.2]paracyclophane reacts with salicylaldehyde or 2-hydroxyacetophenone to yield imines that then give access to a new series of boranils (8b–d) upon complexation with BF2. These novel boron-containing compounds display both planar and axial chiralities and were examined experimentally and computationally. In particular, their photophysical and chiroptical properties were studied and compared to newly prepared, simpler boranils (9a–d) exhibiting axial chirality only. Less sophisticated chiral architectures were shown to demonstrate overall stronger circularly polarized luminescence (CPL) activity

Defining the Effect of the 16p11.2 Duplication on Cognition, Behavior, and Medical Comorbidities

IMPORTANCE The 16p11.2 BP4-BP5 duplication is the copy number variant most frequently associated with autism spectrum disorder (ASD), schizophrenia, and comorbidities such as decreased body mass index (BMI). OBJECTIVES To characterize the effects of the 16p11.2 duplication on cognitive, behavioral, medical, and anthropometric traits and to understand the specificity of these effects by systematically comparing results in duplication carriers and reciprocal deletion carriers, who are also at risk for ASD. DESIGN, SETTING, AND PARTICIPANTS This international cohort study of 1006 study participants compared 270 duplication carriers with their 102 intrafamilial control individuals, 390 reciprocal deletion carriers, and 244 deletion controls from European and North American cohorts. Data were collected from August 1, 2010, to May 31, 2015 and analyzed from January 1 to August 14, 2015. Linear mixed models were used to estimate the effect of the duplication and deletion on clinical traits by comparison with noncarrier relatives. MAIN OUTCOMES AND MEASURES Findings on the Full-Scale IQ (FSIQ), Nonverbal IQ, and Verbal IQ; the presence of ASD or other DSM-IV diagnoses; BMI; head circumference; and medical data. RESULTS Among the 1006 study participants, the duplication was associated with a mean FSIQ score that was lower by 26.3 points between proband carriers and noncarrier relatives and a lower mean FSIQ score (16.2-11.4 points) in nonproband carriers. The mean overall effect of the deletion was similar (-22.1 points; P 100) compared with the deletion group (P < .001). Parental FSIQ predicted part of this variation (approximately 36.0% in hereditary probands). Although the frequency of ASD was similar in deletion and duplication proband carriers (16.0% and 20.0%, respectively), the FSIQ was significantly lower (by 26.3 points) in the duplication probands with ASD. There also were lower head circumference and BMI measurements among duplication carriers, which is consistent with the findings of previous studies. CONCLUSIONS AND RELEVANCE The mean effect of the duplication on cognition is similar to that of the reciprocal deletion, but the variance in the duplication is significantly higher, with severe and mild subgroups not observed with the deletion. These results suggest that additional genetic and familial factors contribute to this variability. Additional studies will be necessary to characterize the predictors of cognitive deficits

Synthèse et étude de la réactivité de nouveaux allylboronates alpha-hétérosubstitués

Over the last thirty years, allylboranes, a particular class of organoboron compounds, have found many valuable applications in organic synthesis, mainly in the stereoselective synthesis of homoallylic alcohols via addition to aldehydes. In this context, we have developed two novel families of alpha-heterosubstituted allylboronates. We first studied the behavior of gamma-borylallylsilanes towards various electrophilic species in order to access to alpha-fluoroallylboronates which are versatile precursors of various fluorinated molecules. Other heteroatom or carbon electrophiles could also be used to afford after refunctionalization with aldehydes structurally diverse unsaturated alcohols. In the second part of this thesis, we studied the reactivity of alpha-isocyanatoallylboronates prepared by [3,3] sigmatropic rearrangement of borylated allylcyanates. These intermediates have proven to be particularly useful to synthesize optically active cyclic seven membered enecarbamates and tetrasubstituted pyrrolidines.Au cours de ces trente dernières années, les allylboranes, une classe particulière de composés organoborés, ont pris une place particulièrement importante en synthèse organique, principalement dans la synthèse stéréocontrôlée d'alcools homoallyliques par addition sur un aldéhyde. C'est dans ce contexte que s'inscrit mon travail de thèse qui a pour objectif la mise au point de voies d'accès originales à deux familles d'allylboronates alpha-hétérosubstitués et à l'étude de leur réactivité. Pour cela, nous nous sommes intéressés dans un premier temps au comportement de gamma-borylallylsilanes vis à vis de diverses espèces électrophiles, ce qui a permis d'accéder notamment à des alpha-fluoroallylboronates, précurseurs de (Z)-1-fluoro-1-alcènes et à des fluorures allyliques. D'autres électrophiles, hétéroatomiques ou carbonés, peuvent être utilisés pour conduire après refonctionnalisation par addition sur des aldéhydes à des alcools insaturés de structures variées. Dans une seconde partie, nous avons synthétisé des alpha-isocyanatoallylboronates par réarrangement sigmatropique [3,3] d'allylcyanates borylés. Ces intermédiaires réactionnels, particulièrement intéressants pour accéder en série optiquement active à des ènecarbamates cycliques à sept chaînons, sont également précurseurs de pyrrolidines tétrasubstituées selon un réarrangement jusqu'alors non décrit dans la littérature

Synthesis and study of the reactivity of new allylboronates alpha-heterosubstituted

Au cours de ces trente dernières années, les allylboranes, une classe particulière de composés organoborés, ont pris une place particulièrement importante en synthèse organique, principalement dans la synthèse stéréocontrôlée d'alcools homoallyliques par addition sur un aldéhyde. C'est dans ce contexte que s'inscrit mon travail de thèse qui a pour objectif la mise au point de voies d'accès originales à deux familles d'allylboronates alpha-hétérosubstitués et à l'étude de leur réactivité. Pour cela, nous nous sommes intéressés dans un premier temps au comportement de gamma-borylallylsilanes vis à vis de diverses espèces électrophiles, ce qui a permis d'accéder notamment à des alpha-fluoroallylboronates, précurseurs de (Z)-1-fluoro-1-alcènes et à des fluorures allyliques. D'autres électrophiles, hétéroatomiques ou carbonés, peuvent être utilisés pour conduire après refonctionnalisation par addition sur des aldéhydes à des alcools insaturés de structures variées. Dans une seconde partie, nous avons synthétisé des alpha-isocyanatoallylboronates par réarrangement sigmatropique [3,3] d'allylcyanates borylés. Ces intermédiaires réactionnels, particulièrement intéressants pour accéder en série optiquement active à des ènecarbamates cycliques à sept chaînons, sont également précurseurs de pyrrolidines tétrasubstituées selon un réarrangement jusqu'alors non décrit dans la littérature.Over the last thirty years, allylboranes, a particular class of organoboron compounds, have found many valuable applications in organic synthesis, mainly in the stereoselective synthesis of homoallylic alcohols via addition to aldehydes. In this context, we have developed two novel families of alpha-heterosubstituted allylboronates. We first studied the behavior of gamma-borylallylsilanes towards various electrophilic species in order to access to alpha-fluoroallylboronates which are versatile precursors of various fluorinated molecules. Other heteroatom or carbon electrophiles could also be used to afford after refunctionalization with aldehydes structurally diverse unsaturated alcohols. In the second part of this thesis, we studied the reactivity of alpha-isocyanatoallylboronates prepared by [3,3] sigmatropic rearrangement of borylated allylcyanates. These intermediates have proven to be particularly useful to synthesize optically active cyclic seven membered enecarbamates and tetrasubstituted pyrrolidines

Interactive competitive breadth-first exploration for sketch interpretation

International audienceIn this paper, we present a new generic method for an interactive interpretation of sketches. This method is based on a competitive breadth-first exploration of the analysis tree. As opposed to well known structural approaches, this method allows to evaluate simultaneously several possible hypotheses of recognition in a dynamic local context of document. At each step of the analysis, the decision process selects the best hypotheses. If it detects an ambiguity, it will solicit the user to select the right hypothesis. In fact, the user participation has a great impact to avoid error accumulation during the analysis step and overcomes the combinatory due to the sketch complexity. This paper demonstrates this interactive method on 2D architectural floor plans

Ring trial on comparison of articial digestion methods for detection of encapsulated Trichinella spiralis larvae in porkmeat

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Ring trial on comparison of articial digestion methods for detection of encapsulated Trichinella spiralis larvae in porkmeat

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Ene reactions of 2-borylated α-methylstyrenes a practical route to 4-methylenechromanes and derivatives

International audience4-Methylenechromanes were prepared via a three-step process from 2-borylated -methylstyrenes. This sequence is based on a key glyoxylate-ene reaction catalyzed by scandium(III) triflate. The resulting -hydroxy boronates, which cyclise to seven-membered homologues of benzoxaborole on silica gel, were cleanly oxidized with sodium perborate, then cyclised under Mitsunobu conditions. Additionally, several further functional transformations of 4-methylenechromanes or their precursors were carried out to illustrate the synthetic potential of these intermediates

[3,3]-Sigmatropic rearrangement of boronated allylcyanates: a new route to α-aminoboronate derivatives and trisubstituted tetrahydrofurans.

International audience[3,3]-Sigmatropic cyanate-isocyanate rearrangement provides a powerful tool for the preparation of α-isocyanato allylboronic esters, which can be further trapped with a variety of nucleophiles. Hydrogenation gave the corresponding α-aminoboronates derivatives while addition of aldehydes afforded homoallylic alcohols, (tetrahydrofuran-2-yl)carbamate, ether, or urea derivatives

Emergence of the trematode Alaria alata in wild boar in France

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