Arylboration of Enecarbamates for the Synthesis of Borylated Saturated N-Heterocycles.

Two catalytic systems have been developed for the arylboration of endocyclic enecarbamates to deliver synthetically versatile borylated saturated N-heterocycles in good regio- and diastereoselectivities. A Cu/Pd dual catalytic reaction enables the synthesis of borylated, α-arylated azetidines, while a Ni-catalysed arylboration reaction efficiently functionalizes 5-, 6-, and 7-membered enecarbamates. In the case of the Cu/Pd-system, a remarkable additive effect was identified that allowed for broader scope. The products are synthetically useful, as demonstrated by manipulations of the boronic ester to access biologically active compounds.

Radical philicity and its role in selective organic transformations.

Radical intermediates in organic chemistry lack a full octet of electrons and, thus, are commonly said to be electron deficient. By denotation, such a statement is technically correct; however, in modern literature, the term 'electron deficient' carries a connotation of electrophilicity. This lexical quirk leads one to predict that all radicals should behave as electrophiles, when this is not the case. Indeed, practitioners of radical chemistry have known for decades that many radicals behave as nucleophiles, sometimes strongly so. This Review aims to establish guidelines for understanding radical philicity by highlighting examples from recent literature as a demonstration of general reactivity paradigms across a series of different carbon-based and heteroatom-based radicals. We present strategies for predicting the philicity of a given radical on the basis of qualitative features of the radical's structure. Finally, we discuss the implications of radical philicity to selective hydrogen atom transfer.