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Reactions of Di(tert-butyl)diazomethane with Acceptor-Substituted Ethylenes

✍ Scribed by Rolf Huisgen; Peter Pöchlauer; Grzegorz Mlostoń; Kurt Polborn

Publisher
John Wiley and Sons
Year
2007
Tongue
German
Weight
187 KB
Volume
90
Category
Article
ISSN
0018-019X

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✦ Synopsis

Abstract

Di(__tert‐butyl)diazomethane (4) is a nucleophilic 1,3‐dipole with strong steric hindrance at one terminus. In its reaction with 2,3‐bis(trifluoromethyl)fumaronitrile ((E)‐BTE), a highly electrophilic tetra‐acceptor‐substituted ethene, an imino‐substituted cyclopentene 9 is formed as a 1 : 2 product. The open‐chain zwitterion 10, assumed as intermediate, adds the second molecule of (E)‐BTE. The ^19^F‐ and ^13^C‐NMR spectra allow the structural assignment of two diastereoisomers, 9A and 9B. The zwitterion 10 can also be intercepted by dimethyl 2,3‐dicyanofumarate (11) and furnishes diastereoisomeric cyclopentenes 12A and 12B; an X‐ray‐analysis of 12B confirms the ‘mixed’ 1 : 1 : 1 product. Competing is an (E)‐BTE‐catalyzed decomposition of 4 to give 2,3,4,4‐tetramethylpent‐1‐ene (7)+N~2~; the reaction of (E)‐BTE with a trace of water appears to be responsible for the chain initiation. The H~2~SO~4~‐catalyzed decomposition of diazoalkane 4, indeed, produced the alkene 7 in high yield. The attack on the hindered diazoalkane 4 by 11 is slower than that by (E)‐BTE; the zwitterionic intermediate 21 undergoes cyclization and furnishes the tetrasubstituted furan 22. In fumaronitrile, electrophilicity and steric demand are diminished, and a 1,3‐cycloaddition produces the 4,5‐dihydro‐1__H‐pyrazole derivative 25. The reaction of 4 with dimethyl acetylenedicarboxylate leads to pyrazole 29+isobutene.

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