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Scientific article
English

Addition of Carbon Nucleophiles to Tricarbonylchromium Complexes of 1,2-Dihydrocyclobutabenzene, Indane, 1,2,3,4-Tetrahydronaphthalene and <i>ortho</i>-Xylene

Published inHelvetica chimica acta, vol. 74, no. 8, p. 2009-2023
Publication date1991
Abstract

3-Substituted 1,2-dihydrocyclobutabenzenes (bicyclo[4. 2. 0]octa-1,3,5-triene) are readily accessible from [Cr(CO)3(1,2-dihydrocyclobutabenzene)] (1) via a two-step sequence which involves addition of a nucleophile and oxidation of the intermediate anionic cyclohexadienyl complex. Nucleophiles used include LiCMe2CN (A), LiCH2CN (B), LiC(Me)(OR)CN (C),[...], LiCMe2CO2Me (F), and LiCH2CO2(t-Bu) (G). [Cr(CO)3(Indane)] (2) also reacts highly regioselectively to give a-substitution, whereas [Cr(CO)3(tetrahydronaphthalene)] (3) and [Cr(CO)3(o-xylene)] (4) give mixtures of products. In several cases, the mixtures of the intermediate anionic cyclohexadienyl complexes can be equilibrated to give, after oxidation, ß-substituted derivatives of 1,2,3,4-tetrahydronaphthalene and ortho-xylene selectively. EHMO calculations were carried out, and they rationalize the observed a-regioselectivity of nucleophilic addition under kinetic control, The X-ray structures of 1 and 4 are reported and in both compounds the Cr(CO)3 group adopts in the solid state a staggered syn-conformation with respect to the substituted aromatic C-atonis.

Citation (ISO format)
KUNDIG, Ernst Peter et al. Addition of Carbon Nucleophiles to Tricarbonylchromium Complexes of 1,2-Dihydrocyclobutabenzene, Indane, 1,2,3,4-Tetrahydronaphthalene and &lt;i&gt;ortho&lt;/i&gt;-Xylene. In: Helvetica chimica acta, 1991, vol. 74, n° 8, p. 2009–2023. doi: 10.1002/hlca.19910740836
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ISSN of the journal0018-019X
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