Organometallic reactions of α-haloimines as a useful tool in organic synthesis

The reaction of organometallic reagents, e.g. alkyllithiums, cuprates and alkylcoppers, with α-haloimines gave selectively a variety of synthetically useful reactions, including coupling to 1,4-diimines, homologation, and production of heterocycles.     

New synthesis of 2-substituted resorcinols

By aromatization of 2-methyl-, 2-benzyl- and 2-acetyl-2-chloro-1,3-cyclohexanedione in dimethylforamide-hydrogen chloride 25%, respectively 2-methyl-, 2-benzyl and 2-acetylresorcinol were obtained in high yields.     

Friedel-crafts reaction of α-chloroaldimines : possible intermediacy of α-imidoylcarbenium ions

α-Chloroaldimines are arylated at the α-position under Friedel-Crafts conditions via intermediacy of α-imidoylcarbenium ions.     

Formation of α-iminoketones and α-diimines from aliphatic α,α′-dibromoketones

A novel reaction of aliphatic α,α′-dibromoketones with primary amines has been found to produce α-iminoketones and/or α-diimines, which can be selectively obtained under appropriate reaction conditions.     

Regiospecific nucleophile-induced fragmentation of α,α-dichloro-β-iminocarbonyl compounds

The reaction of α,α-dichloro-β-(N-alkyl or N-aryl)iminocarbonyl compounds with nucleophiles resulted in a regiospecific fragmentation to afford α,α-dichloroketimines.     

A Facile Synthesis of 1,2-Disubstituted Aziridines

In spite of the fact that a number of methods are available for the preparation of aziridines, general synthetic routes leading to 1,2-disubstituted aziridines remained laborious in most cases^(2-6). A convenient and versatile synthesis is desirable in order to permit studies of this important biologically active heterocyclic system.     

A unique and highly remarkable boron Trifluoride catalyzed rearrangement Of 2,2-di-t-butyloxirane into 2,2,3,3,4,4-hexamethyltetrahydrofuran

-The boron trifluoride catalyzed rearrangement of 2,2-di-t-butyloxirane, involving competitive reactions of transient carbenium ions, could be selectively directed towards either 2,2,3,3,4,4- hexamethyltetrahydrofuran or 2-t-butyl-2,3-dimethyl-3-buten-1-ol. Hydride shift to afford 2,2-di-t-butylacetaldehyde was only observed to a minor extent.     

Reactivity of α,α-Dihalogenated Imino Compounds. Part VIII1. Aziridine Formation by Lithium Aluminium Hydride Reduction of N-2-(1,1-Dichloroalkylidene) Cyclohexylamines

1,2-Disubstituted aziridines 2 are not readily accessible and most syntheses remain laborious³. We recently reported⁴ that reaction of α,α-dihalogenated aldimines with lithium aluminium hydride provided a facile synthesis of 1,1-disubstituted aziridines (a three step synthesis starting from ordinary aliphatic aldehydes).     

Synthesis of α-Halogenated Imidoyl Cyanides1

As part of our investigations in the field of the α-halogenated imine chemistry,¹ we describe herein a convenient and general synthesis of aliphatic α-halogenated imidoyl cyanides 1 (X=Cl,Br). From the synthetic and mechanistic point of view, compounds 1 are expected to exhibit interesting features due to the presence of three functional groups in the molecule.