The synthesis of 1,2-diamines via a Rh-catalyzed intermolecular hydroamination of N-allyl imines with cyclic amines is presented. Coordinating groups proximal to the olefin bind to the catalyst and promote the transformation. The reaction affords 1,2-diamines in very good yields and is functional-group-tolerant and highly diastereoselective.
The development of an anti-Markovnikov-selective hydroamination of unactivated alkenes is a significant challenge in organometallic chemistry. Herein, we present the rhodium-catalyzed anti-Markovnikov-selective hydroamination of homoallylic amines. The proximal Lewis basic amine serves to promote reactivity and enforce regioselectivity through the formation of the favored metallacycle, thus over-riding the inherent reactivity of the alkene. The scope of both the amine nucleophiles and homoallylic amines that participate in the reaction is demonstrated.
Vicinal diamines are a common motif found in biologically active molecules. The hydroamination of allyl amine derivatives is a powerful approach for the synthesis of substituted 1,2-diamines. Herein, the rhodium-catalyzed hydroamination of primary and secondary allylic amines using diverse amine nucleophiles, including primary, secondary, acyclic, and cyclic aliphatic amines to access a wide range of unsymmetrical vicinal diamines, is presented. The utility of this methodology is further demonstrated through the rapid synthesis of several bioactive molecules and analogs.
The
Ir-catalyzed regioselective hydroamination of allyl amines
as well as the catalyst-controlled regiodivergent hydroamination of
homoallylic amines with aniline nucleophiles is reported. These directed
hydroamination reactions afford a variety of 1,2-, 1,3-, and 1,4-diamines
in good to excellent yields and high regio- and chemoselectivities.
Mechanistic investigations suggest that the reactions are proceeding
through an oxidative addition into the ArHN–H bond and that
the observed regioselectivity is due to the selective formation of
a five- or six-membered metallacyclic intermediate depending on the
catalyst employed.
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