ABSTRACT
Described here is a method for intermolecular hydroalkoxylation and hydrocarboxylation of 2-azadienes through cobalt-catalyzed hydrogen atom transfer and oxidation. This protocol provides a source of 2-azaallyl cation equivalents under mild conditions, is chemoselective in the presence of other CâC double bonds, and requires no excess amount of added alcohol or oxidant. Mechanistic studies suggest that the selectivity arises from lowering the transition state that leads to the highly stabilized 2-azaallyl radical.
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 product with 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.
ABSTRACT
We have developed a Rh(III)-catalyzed diastereoselective [2+1] annulation onto allylic alcohols initiated by alkenyl C-H activation of N-enoxyphthalimides to furnish substituted cyclopropyl-ketones. Notably, the traceless oxyphthalimide handle serves three functions: directing C-H activation, oxidation of Rh(III), and, collectively with the allylic alcohol, in directing cyclopropanation to control diastereoselectivity. Allylic alcohols are shown to be highly reactive olefin coupling partners leading to a directed diastereoselective cyclopropanation reaction, providing products not accessible by other routes.
Subject(s)
Coordination Complexes/chemistry , Cyclopropanes/chemical synthesis , Ketones/chemical synthesis , Propanols/chemistry , Rhodium/chemistry , Alkenes/chemistry , Catalysis , Cyclization , StereoisomerismABSTRACT
We have developed a Rh(III)-catalyzed cyclopropanation of unactivated olefins initiated by an alkenyl C-H activation. A variety of 1,1-disubstituted olefins undergo efficient cyclopropanation with a slight excess of alkene stoichiometry. A series of mechanistic interrogations implicate a metal-carbene as an intermediate.
ABSTRACT
Utilizing rhodium catalysis, aryl nucleophiles generated via carbon-carbon single bond activation successfully undergo oxidative coupling with Michael acceptors. The reaction scope encompasses a broad range of nucleophiles generated from quinolinyl ketones as well as a series of electron deficient terminal alkenes, illustrating the broad potential of intersecting carbon-carbon bond activation with synthetically useful coupling methodologies. The demonstrated oxidative coupling produces a range of cinnamyl derivatives, several of which are challenging to prepare via conventional routes.