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Chemie freier, cyclischer vicinaler Tricarbonyl‐Verbindungen (`1,2,3‐Trione'), Teil 1, Reaktionsweise von Diazomethan und seinen Derivaten mit 5,5‐Dimethylcyclohexan‐1,2,3‐trion (=`Oxo‐dimedon') und verwandten Cyclohexan‐1,2,3‐trionen
Author(s) -
Schank Kurt,
La Vecchia Luigi,
Lick Carlo
Publication year - 2001
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 - 10.1002/1522-2675(20010711)84:7<2071::aid-hlca2071>3.0.co;2-d
Subject(s) - chemistry , diazomethane , nucleophile , electrophile , medicinal chemistry , aryne , vicinal , cyclohexane , redox , organic chemistry , catalysis
Abstract Chemistry of Free Cyclic Vicinal Tricarbonyl Compounds (`1,2,3‐Triones'). Part 1. Reaction of Diazomethane and Its Derivatives with 5,5‐Dimethylcyclohexane‐1,2,3‐trione (=`Oxo‐dimedone') and Related Cyclohexane‐1,2,3‐triones Interactions of diazomethane and of its derivatives as typical nucleophiles with cyclic 1,2,3‐triones as efficient electrophiles lead to different results: a ) formation of oxiranes (C,O insertion under loss of N 2 ), b ) nucleophilic addition yielding diazoaldols, c ) formation of ring‐enlargement products (C,C insertion under loss of N 2 ), and d ) formation of dioxoles via redox reactions (under loss of N 2 ). Our results and those of other groups allow us to recognize that the unexpected outcome of the reaction of oxodimedone and several related species is due to a closed‐shell diazoaldol formation followed by an open‐shell redox reaction leading to dioxoles.