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Cycloadducts from Diazocumulenes and 1,2,3(λ3)-Diazaphospholes: Thermolysis Generates Products Derived from 3-Alkenylidene-1,2,3(λ5)-diazaphospholes

✍ Scribed by Jochen Kerth; Gerhard Maas

Publisher
John Wiley and Sons
Year
1999
Tongue
English
Weight
462 KB
Volume
1999
Category
Article
ISSN
1434-193X

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✦ Synopsis

Diazo-2-oxoalkyl)silanes 1 react with 2-acyl-1,2,3(λ 3 )-[3+2] cycloreversion into 2 and 4, and extrusion of molecular nitrogen. The latter process is likely to generate 3-diazaphospholes 4 to form [3+2] cycloaddition products 5, which indicate that 1-diazo-2-silyloxy-1-alkenes 2, alkenylidene-1,2,3(λ 5 )-diazaphospholes 8, which are trapped intermolecularly by diazaphospholes 4. Intermediates 8 coexisting with 1 as the minor equilibrium component, have been trapped. Thermal impact on cycloadducts 5 generates could not be intercepted with dimethyl acetylenedicarboxylate (DMAD); rather, 5i reacts with DMAD to form the tricyclic phosphorus heterocycles 9; their formation can be rationalized by two competing processes, namely thermal the spiro-λ 5 -phosphorane 11 in low yield.

criteria, [5] the participation of their PϭC bond in cycload- [a

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