Sulfamides direct radical-mediated chlorination of aliphatic C-H bonds.

Given the prevalence of aliphatic amines in bioactive small molecules, amine derivatives are opportune as directing groups. Herein, sulfamides serve as amine surrogates to guide intermolecular chlorine-transfer at γ-C(sp) centers. This unusual position-selectivity arises because accessed sulfamidyl radical intermediates engage preferentially in otherwise rare 1,6-hydrogen-atom transfer (HAT) processes through seven-membered transition states.

Iron(MCP) Complexes Catalyze Aziridination with Olefins As Limiting Reagents.

Herein described are the first efficient nitrogen-atom transfer reactions mediated by iron N, N'-dimethyl- N, N'-bis(2-pyridinylmethyl)cyclohexane-1,2-diamine- (MCP-) and 2-({1-[(pyridin-2-ylmethyl)pyrrolidin-2-yl]pyrrolidin-1-yl}methyl)pyridine-type (PDP-type) complexes. These catalysts affect styrene aziridination under mild conditions based on a limiting quantity of olefin substrate.