Recent Applications of α-Metalated Isocyanides in Organic Synthesis

Being both nucleophilic and electrophilic, α-metalated isocyanides can add to polar double bonds, forming heterocycles. They are also synthons for α-metalated primary amines. This article describes recent or improved procedures for their use in organic synthesis: (1) In heterocyclic syntheses to give 2-oxazolines, 2-imidazolines, 2-thiazolines, oxazoles and oligooxazoles, thiazoles, triazoles, imidazolinones, pyrroles, 5,6-dihydro-1,3-oxazines and -thiazines, and (via cycloaddition with nitrones) 2-imidazolidinones. (2) In the field of formylaminomethylenation, for example transformation of estrone methyl ether and a keto sugar into the corresponding α-formylaminoacrylic esters, and the conversion of aldehydes and ketones by 3- and 4-pyridyl-methyl isocyanides into N-(1-pyridyl-1-alkenyl)formamides and their hydrolysis to 3- and 4-acylpyridines. (3) In connection with the use of α-metalated isocyanides as synthons for α-metalated primary amines, the author demonstrates how they may be used for preparation of 1,2- and 1,3-amino alcohols, 1,2-diamines, 2,3-diaminoalkanoic acids and for synthesis of higher amino acids starting from simple amino acids.     

Enamines. 41. A new synthesis of α-amino-pyrroles

Diimmonium salt 1 reacts with enamines 3 affording α-amino-pyrroles 4 . The synthetic potential of this reaction is discussed.     

α-Metalated Isocyanides in Organic Synthesis. New synthetic methods (6)

α-Alkali-metalated isocyanides, which can be obtained from isocyanides and bases, can be used for nucleophilic introduction of (masked) α-aminoalkyl groups. Intramolecular ring-closure may then follow if a nucleophile combines at the electron sextet of the isocyanide carbon. Treatment of α-alkali-metalated isocyanides with electrophilic agents permits rapid and efficient synthesis of, inter alia, 2- and 3-amino alcohols, straight-chain, branched, and β-functional α-amino acids, olefins, vinyl isocyanides, and of a large number of mainly five-, but also six- and seven-membered aza-, diaza-, oxa-aza-, and thia-aza heterocycles.     

A novel synthesis of α-hydroxy- and α,α′-dihydroxyketone from α-iodo and α,α′-diiodo ketone using photoirradiation

A novel reaction of α-iodo ketone (α-iodocycloalkanone, α-iodo-β-alkoxy ester, and α-iodoacyclicketone) with irradiation under a high-pressure mercury lamp gave the corresponding α-hydroxyketone in good yields. In the case of α,α′-diiodo ketone, α,α′-dihydroxyketone which little has been reported until now was obtained. This reaction affords a new, clean and convenient synthetic method for α-hydroxy- and α,α′-dihydroxyketone.