✍ Scribed by Gabriel García-Gómez; Josep M. Moretó
No coin nor oath required. For personal study only.
Fifteen α,ω-dienals and one α-en-ω-ynal were prepared. These substrates were treated with Ni(COD) 2 /TMSCl under carbonylative and noncarbonylative conditions, with subsequent methanol quenching of the resulting metal intermediates to afford different types of cycloadducts. From the compounds thus obtained, it is concluded that the reaction proceeds through an intermediate (π-allyl)Ni complex, which readily cyclises in a ''metallo-ene''-type reaction. The different pathways were characterised by further carbonyl insertion or by protonolysis, resulting either in cyclopentanone
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The synthesis of heterotelechelic poly(methyl methacrylate) (PMMA) containing ␣-maleimide--dienyl end-groups and its subsequent intramolecular cyclization are described. The anionic polymerization of methyl methacrylate was carried out with 3-tert-butyldimethylsilyloxypropyl-1-lithium and 5-bromo-1,