Reactivity of (3-chloro-2-methylenecycloalkyl)palladium chloride dimers: Nucleophilic attack by one or two equivalents of malonate anion.

✍ Scribed by William A Donaldson; Valerie J Grief

• Publisher: Elsevier Science
• Year: 1986
• Tongue: French
• Weight: 296 KB
• Volume: 27
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(00)84525-6

✦ Synopsis

The title compounds undergo reaction with one and two equivalents of malonate anion in the presence of phosphine ligands to afford mono-and di-substituted products.

A mechanism for the formation of both products is presented. We' and others' have recently shown that the chloropalladation of Q-methylenebicyclo[n.l.O]alkanes 1 affords (3-chloro-Z-methylenecycloalkyl)palladium chloride dimers z in high yields. Since compounds l_ may be prepared from the corresponding cyclic olefins (J)ly3 these two steps constitute a formal ring homologation methodology. Because of the great potential for elaboration of the n-ally1 moiety,4 we investigated the reactivity of compounds E as the final step in an overall ring homologation-functionalization methodology. Our initial results on the basic cleavage of compounds 2 indicates that they react as "1,3-doubly activated" n-allyls.' Recent conflicting accounts of the reactivity of "l,l-diactivated" n-allyls 697 with carbon nucleophiles as well as the reactivity of other "1,4_diactivated" n-allyls systems (2 and fl)8'g have been reported.