ABSTRACT
The first stereoselective rhodium-catalyzed intermolecular aziridination and C-H amination of alkenes to produce chiral carbamate-protected aziridines and allylic amines is described. Good yields and diastereoselectivities were achieved using a readily available chiral N-tosyloxycarbamate and stoichiometric amount of the alkene substrate. Furthermore the protecting group is easy to cleave under mild reaction conditions.
Subject(s)
Alkenes/chemistry , Aziridines/chemistry , Rhodium/chemistry , Amination , Aziridines/chemical synthesis , Carbamates/chemical synthesis , Carbamates/chemistry , Catalysis , Combinatorial Chemistry Techniques , Molecular Structure , StereoisomerismSubject(s)
Drug Design , Enzyme Inhibitors/pharmacology , GTP-Binding Proteins/antagonists & inhibitors , Transglutaminases/antagonists & inhibitors , Enzyme Inhibitors/chemical synthesis , Enzyme Inhibitors/classification , Enzyme Inhibitors/metabolism , Epoxy Compounds/chemical synthesis , Epoxy Compounds/chemistry , Epoxy Compounds/pharmacology , GTP-Binding Proteins/metabolism , Humans , Isoxazoles/chemical synthesis , Isoxazoles/chemistry , Isoxazoles/pharmacology , Ketones/chemical synthesis , Ketones/chemistry , Ketones/pharmacology , Models, Biological , Molecular Probes/chemical synthesis , Molecular Probes/chemistry , Molecular Targeted Therapy/methods , Protein Glutamine gamma Glutamyltransferase 2 , Transglutaminases/metabolismABSTRACT
The reaction of a chloroformate or di-tert-butyl dicarbonate and sodium azide with an aromatic carboxylic acid produces the corresponding acyl azide, presumably through the formation of an azidoformate. The acyl azide undergoes a Curtius rearrangement to form an isocyanate derivative which is trapped either by an alkoxide or by an amine to form the aromatic carbamate or urea. The reaction conditions are compatible with a variety of functional groups and allow the synthesis of a number of aniline derivatives containing alkyl, halide, nitro, ketone, ether, and thioether substituents. [reaction: see text]
Subject(s)
Aniline Compounds/chemistry , Carboxylic Acids/chemistry , Urea/analogs & derivatives , Urea/chemistry , Benzoates/chemistry , Indicators and ReagentsABSTRACT
[reaction: see text] The reaction of a carboxylic acid with di-tert-butyl dicarbonate and sodium azide allowed the formation of an acyl azide intermediate, which undergoes a Curtius rearrangement in the presence of tetrabutylammonium bromide and zinc(II) triflate. The trapping of the isocyanate derivative in the reaction mixture led to the desired tert-butyl carbamate in high yields at low temperature. These reaction conditions are compatible with a variety of substrates, including malonate derivatives, which provide access to protected amino acids.
