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Addition and Ring Expansion Reactions of Tricarbonyl(1,2-dioxobenzocyclobutene)chromium(0) with Carbon Nucleophiles – Unexpected Formation of Benzocycloheptene Derivatives and the First Head-to-Head Coupling of Two Methoxyallene Molecules

✍ Scribed by Beate Voigt; Michael Brands; Richard Goddard; Rudolf Wartchow; Holger Butenschön


Publisher
John Wiley and Sons
Year
1998
Tongue
English
Weight
216 KB
Volume
1998
Category
Article
ISSN
1434-193X

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✦ Synopsis


Addition of carbon nucleophiles to (benzocyclobutene-

Cope rearrangement followed by an intramolecular aldol addition. This is also the case with lithiated methoxyallene, dione)tricarbonylchromium(0) (4) results in the formation of exo mono-and diadducts as well as 1,2-diketones as the and as the result the first head-to-head coupling product 12 of two methoxyallene molecules is isolated in good yield. 12 consequence of proximal ring-opening reactions. In one case the unexpected formation of benzocycloheptenedione is used as a diene in Diels-Alder cycloadditions, and its molecular structure is compared to that of the similar complexes is observed. Treatment of 4 with an excess of 1ethoxy-1-lithioethene gives the product of a dianionic oxy-molecule 13, lacking the two exo methylene substitutents.