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Studies on the Reactivity of α ‐Cyano‐ α ‐isocyanoalkanoates – Versatile Synthons for the Assembly of Imidazoles
Author(s) -
Bergemann Marco,
Neidlein Richard
Publication year - 1999
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/(sici)1522-2675(19990609)82:6<909::aid-hlca909>3.0.co;2-t
Subject(s) - chemistry , synthon , reactivity (psychology) , cleavage (geology) , alkyl , carbamate , alkoxy group , molecule , combinatorial chemistry , primary (astronomy) , organic chemistry , medicinal chemistry , medicine , alternative medicine , geotechnical engineering , physics , pathology , astronomy , fracture (geology) , engineering
The reactivity and the synthetic potential of α ‐cyano‐ α ‐isocyanoalkanoates 2 were investigated. Interestingly, reaction of 2 with alkoxides gave (alkoxy)(alkyl)imidazoles 5 , whereas the analogous thiolates led to different products, namely substituted 4 H ‐imidazoles 7 , together with compounds 6 , which formed by addition of thiolate to the isocyano group. Primary amines reacted, on one hand, in the same manner as thiolates to form of 4 H ‐imidazoles 10 , and, on the other hand, cleavage of the molecule to the proposed unstable aminoimidazole 8 and the carbamate 9 was observed. Secondary amines add selectively to the isocyano group to form compounds 11 . Like simple isocyanides, α ‐cyano‐ α ‐isocyanoalkanoates 2 can be subjected to [4+1] cycloadditions and multicomponent reactions of the Passerini type. Mechanisms for the described reactions are discussed.