Asymmetric Vicinal and Remote Hydroamination of Olefins by Employing a Heck-Reaction-Derived Hydride Source

Abstract

Metal hydrides are reactive intermediates in numerous catalytic processes. In many catalytic processes, metal hydrides are formed, but their potential reactivity is often wasted by reaction with a base or an oxidant to permit catalyst turnover. In this report, the hydroamination of unactivated olefins is described by coupling a Heck reaction with a hydroamination reaction between aryl boronic acid, olefin, and a nitrene precursor dioxazolone. Initiated by a Heck reaction between the olefin and arylboroic acid, a rhodium hydride intermediate is generated and is retained for the hydroamination of a second equivalent of the olefin. Depending on the chain length of the alkyl group of the olefin, α- or β-amino amides were obtained in excellent regio- and enantioselectivity via direct or remote (migratory) hydroamination, respectively. The coupling system features a broad scope, mild conditions, and excellent enantioselectivity, and it also represents a rare example of asymmetric olefin hydroamination using a chiral rhodium(III) cyclopentadienyl catalyst. Mechanistic studies delineated the turnover-limiting and enantio-determining steps of this catalytic system.