Brain markers of subtraction and multiplication skills in childhood: task-based functional connectivity and individualized structural similarity.

Arithmetic, a high-order cognitive ability, show marked individual difference over development. Despite recent advancements in neuroimaging techniques have enabled the identification of brain markers for individual differences in high-order cognitive abilities, it remains largely unknown about the brain markers for arithmetic. This study used a data-driven connectome-based prediction model to identify brain markers of arithmetic skills from arithmetic-state functional connectivity and individualized structural similarity in 132 children aged 8 to 15 years. We found that both subtraction-state functional connectivity and individualized SS successfully predicted subtraction and multiplication skills but multiplication-state functional connectivity failed to predict either skill. Among the four successful prediction models, most predictive connections were located in frontal-parietal, default-mode, and secondary visual networks. Further computational lesion analyses revealed the essential structural role of frontal-parietal network in predicting subtraction and the essential functional roles of secondary visual, language, and ventral multimodal networks in predicting multiplication. Finally, a few shared nodes but largely nonoverlapping functional and structural connections were found to predict subtraction and multiplication skills. Altogether, our findings provide new insights into the brain markers of arithmetic skills in children and highlight the importance of studying different connectivity modalities and different arithmetic domains to advance our understanding of children's arithmetic skills.

Selective C(sp3 )-N Bond Cleavage of N,N-Dialkyl Tertiary Amines with the Loss of a Large Alkyl Group via an SN 1 Pathway.

Polar disconnection of the C(sp3 )-N bond of N,N-dialkyl-substituted tertiary amines via ammonium species conventionally favored the loss of the smaller alkyl group by an SN 2 displacement, while selective C(sp3 )-N bond cleavage by cutting off the larger alkyl group is still underdeveloped. Herein, we present a novel Pd0 -catalyzed [2+2+1] annulation, proceeding through an alkyne-directed palladacycle formation and consecutive diamination with a tertiary hydroxylamine by cleaving its N-O bond and one C(sp3 )-N bond, for the rapid assembly of tricyclic indoles in a single-step transformation. Noteworthy, experimental results indicated that large tert-butyl and benzyl groups were selectively cleaved via an SN 1 pathway, in the presence of a smaller alkyl group (Me, Et, i Pr). Under the guidance of this new finding, tricyclic indoles bearing a removable alkyl group could be exclusively obtained by using a (α-methyl)benzyl/benzyl or tert-butyl/2-(methoxycarbonyl)ethyl mixed amino source.

Palladium(0)-Catalyzed Intermolecular Carbocyclization of (1,n)-Diynes and Bromophenols: An Efficient Route to Tricyclic Scaffolds.

A novel palladium(0)-catalyzed dearomative cyclization reaction of bromophenols with (1,n)-diynes has been developed for building two new types of tricyclic architectures containing a quaternary carbon center. This method employs inexpensive bromophenols, and easily accessible tethered diynes. It exhibits a broad substrate scope and tolerates various functional groups. Preliminary results with commercially available chiral ligands indicate that enantioselective variants are feasible for both cyclization processes.

A chemo- and regioselective Pd(0)-catalyzed three-component spiroannulation.

A chemo- and regioselective Pd(0)-catalyzed spiroannulation has been successfully developed. The key feature of this method is the use of readily available 1,2-dihaloarenes, alkynes and 2-naphthols for the rapid assembly of spirocarbocyclic molecules. Mechanistic studies revealed that this domino reaction proceeded through a cascade of oxidative addition to Pd(0), alkyne migratory insertion, and 2-naphthol-facilitated dearomatizing [4+1] spiroannulation.