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Über die Reaktion von 2‐Diazo‐1,3‐diketonen mit 1,3‐ambident‐nucleophilen Phosphor‐Yliden: Eine neue Synthese von Monoheteroatom‐Fünf‐ und ‐Sechsringen
Author(s) -
Capuano Lilly,
Drescher Stefan,
Huch Volker
Publication year - 1991
Publication title -
liebigs annalen der chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 0170-2041
DOI - 10.1002/jlac.199119910157
Subject(s) - chemistry , ketene , wittig reaction , diazo , medicinal chemistry , thiophene , ylide , nucleophile , substituent , organic chemistry , catalysis
Reaction of 2‐Diazo‐1,3‐diketones with 1,3‐Ambident‐Nucleophilic Phosphorus Ylides: A New Synthesis of Monoheteroatomic Five‐ and Six‐Membered Rings The thermolysis of 2‐diazo‐1,3‐diketones 1 with 1,3‐ambidentnucleophilic 3‐imino‐ 3 , 3‐thioxo‐ 10 or 3‐oxophosphoanes 11 proceeds either by Wittig reaction, leading to the formation of the pyrrole 7 or thiophene nucleus 12 , or competitively via a mechanism which involves both Wolff rearrangement and Wittig reaction by the acylcarbonyl, whereby 2‐pyridones 8 , 2‐pyrones 14 or the indenyl acetophenone 15 , respectively, are formed. The rates of these processes are strongly determined by substituent effects. As an exception to the general pattern of behavior, the cyclic acyl ketene derived from diazodimedone undergoes Wittig reaction with 3 through the ketene carbonyl, giving the quinoline derivative 9 . The structure of 9 was confirmed by X‐ray diffraction analysis.