Copper-Promoted N-Arylation of the Imidazole Side Chain of Protected Histidine by Using Triarylbismuth Reagents.

The N-arylation of the side chain of histidine by using triarylbismuthines is reported. The reaction is promoted by copper(II) acetate in dichloromethane at 40 °C under oxygen in the presence of diisopropylethylamine and 1,10-phenanthroline and allows the transfer of aryl groups with substituents at any position of the aromatic ring. The reaction shows excellent functional group tolerance and is applicable to dipeptides where the histidine is located at the N terminus. A histidine-guided backbone N-H arylation was observed in dipeptides where the histidine occupies the C terminus.

Visual Attention Saccadic Models Learn to Emulate Gaze Patterns From Childhood to Adulthood.

How people look at visual information reveals fundamental information about themselves, their interests and their state of mind. While previous visual attention models output static 2D saliency maps, saccadic models aim to predict not only where observers look at but also how they move their eyes to explore the scene. In this paper, we demonstrate that saccadic models are a flexible framework that can be tailored to emulate observer's viewing tendencies. More specifically, we use fixation data from 101 observers split into five age groups (adults, 8-10 y.o., 6-8 y.o., 4-6 y.o., and 2 y.o.) to train our saccadic model for different stages of the development of human visual system. We show that the joint distribution of saccade amplitude and orientation is a visual signature specific to each age group, and can be used to generate age-dependent scan paths. Our age-dependent saccadic model does not only output human-like, age-specific visual scan paths, but also significantly outperforms other state-of-the-art saliency models. We demonstrate that the computational modeling of visual attention, through the use of saccadic model, can be efficiently adapted to emulate the gaze behavior of a specific group of observers.

Synthesis of Highly Functionalized Triarylbismuthines by Functional Group Manipulation and Use in Palladium- and Copper-Catalyzed Arylation Reactions.

Organobismuthines are an attractive class of organometallic reagents that can be accessed from inexpensive and nontoxic bismuth salts. Triarylbismuthines are particularly interesting due to their air and moisture stability and high functional group tolerance. We report herein a detailed study on the preparation of highly functionalized triarylbismuth reagents by triple functional group manipulation and their use in palladium- and copper-catalyzed C-, N-, and O-arylation reactions.