Rhodium(III)-Catalyzed Three-Component 1,2-Diamination of Unactivated Terminal Alkenes

Abstract

We report a three-component diamination of simple unactivated alkenes using an electrophilic nitrene source and amine nucleo­philes. The reaction provides rapid access to 1,2-vicinal diamines from terminal alkenes through a one-pot protocol. The transformation proceeds smoothly with excellent tolerance for a broad array of primary and secondary amines, affording the desired products in good yield and regioselectivity. The mechanism is proposed to proceed through a Rh(III)-catalyzed aziridination of alkenes with subsequent ring opening by primary or secondary amines.

The advent of electrophilic hydroxylamine-derived reagents for the direct preparation of unprotected amines

“…77 Recent work by other groups presents additional examples for the construction of heterodiamines via an aziridinium intermediate. [83][84][85] 2.1.3 Masked diamination of alkenes. A direct approach to vicinal diamines with distinguishable amino groups is the installation of a masked amino motif on an alkene along with an amino group.…”

Rh(III)-Catalyzed Three-Component Syn-Carboamination of Alkenes Using Arylboronic Acids and Dioxazolones

“…First, we conducted the reaction under standard conditions, but without phenylboronic acid (Scheme a). As a result, neither N -acyl aziridine nor aziridine ring-opening products are observed after the reaction. This strongly indicates that the Rh­(III)-catalyzed alkene aziridination and subsequent ring-opening with phenylboronic acid is unlikely as the mechanism of the reaction.…”

Diastereoselective Three-Component 3,4-Amino Oxygenation of 1,3-Dienes Catalyzed by a Cationic Heptamethylindenyl Rhodium(III) Complex

“…In search of a potent catalyst to perform the envisioned internal selective oxyamination (Scheme C), this study commenced with an extensive evaluation of Rh­(III) complexes, , whereupon the heptamethylindenyl (Ind*) ligand − was identified as a promising candidate. The initial discovery was made when 4-phenyl-1,3-butadiene ( 1a ) was treated with 3-methyl-1,4,2-dioxazolone ( 3a ) in methanol in the presence of 5 mol % [Ind*RhCl 2 ] 2 and 30 mol % NaF (Table , entry 1).…”