The synthetic utility of tertiary amines to oxidatively generate a-amino radicals is well established, however,p rimary amines remain challenging because of competitive side reactions.T his report describes the site-selective a-functionalization of primary amine derivatives through the generation of a-amino radical intermediates.Employing visible-light photoredox catalysis,p rimary sulfonamides are coupled with electron-deficient alkenes to efficiently and mildly construct CÀCbonds.Interestingly,adivergence between intermolecular hydrogen-atom transfer (HAT) catalysis and intramolecular [1,5] HATwas observed through precise manipulation of the protecting group.T his dichotomyw as leveraged to achieve excellent a/d site-selectivity.

In the presence of AlCl3, a mixture of hydrogen azide and tetramethallyltin underwent 1,4- and subsequently 1,2-addition, respectively, with α,β-unsaturated aldimines to give 1,3-amino azides in good yields. The 1,3-amino azides thus obtained were readily converted into 1,3-diamines by reduction with LiAlH4.

The synthetic utility of tertiary amines to oxidatively generate α‐amino radicals is well established, however, primary amines remain challenging because of competitive side reactions. This report describes the site‐selective α‐functionalization of primary amine derivatives through the generation of α‐amino radical intermediates. Employing visible‐light photoredox catalysis, primary sulfonamides are coupled with electron‐deficient alkenes to efficiently and mildly construct C−C bonds. Interestingly, a divergence between intermolecular hydrogen‐atom transfer (HAT) catalysis and intramolecular [1,5] HAT was observed through precise manipulation of the protecting group. This dichotomy was leveraged to achieve excellent α/δ site‐selectivity.

No abstract

Azides P 0095Double Nucleophilic Addition of Azide and Tetramethallyltin to α,β-Unsaturated Aldimines Promoted by Aluminum Chloride. -A rapid access to 1,3-amino azides such as (V)/(VI) by double nucleophilic addition of tetramethallyltin (II) and HN3 to appropriate α,β-unsaturated aldimines is described. The amino azides thus obtained are readily converted to corresponding 1,3-diamines [cf. (VII)] by reduction with LiAlH4. -(SHIMIZU*, M.; YAMAUCHI, C.; OGAWA, T.; Chem. Lett. 33 (2004) 5, 606-607; Dep. Chem. Mater., Fac. Eng., Mie Univ., Tsu, Mie 514, Japan; Eng.) -M. Schroeter 41-072