Base-Mediated Site-Selective Hydroamination of Alkenes.

We present a base-mediated hydroamination protocol, using substoichiometric amounts of a hydrosilane and potassium tert -butoxide-, that operates under mild conditions at 30 °C. Many aryl- and heteroatom-substituted olefins as well as arylamines are tolerated, affording the desired products with complete regioselectivity. Preliminary mechanistic investigations reveal a non-radical pathway for hydroamination. A sequential remote hydroamination strategy involving an initial Fe-catalysed olefin isomerisation followed by our base-mediated hydroamination was also developed to directly access β-arylamines from terminal aliphatic alkenes. [ABSTRACT FROM AUTHOR]