Reactivity of (3-chloro-2-methylenecycloalkyl)palladium Chloride Dimers: Addition of Stabilized Carbon Nucleophiles and Application to Cyclopentannulation and Cyclohexannulation

Authors

William Donaldson, Marquette UniversityFollow
Jinkang Wang, Marquette University
Valerie G. Cepa, Marquette University
John D. Suson, Marquette University

Document Type

Article

Language

eng

Publication Date

1989

Publisher

American Chemical Society

Source Publication

The Journal of Organic Chemistry

Source ISSN

0022-3263

Abstract

The titie compounds react as either “trimethylenemethane dication” synthons or “isoprenyl monocation" synthons with stabilized carbon nucleophiles in the presence of phosphine ligands. This reactivity is dependent on size of the carbocyclic ring, substituents on the ring, the amount and nature of the nucleophile, and the nature of the phosphine ligand. The product (4a) from alkylation of 2 equiv of malonate anion with (3-chloro-2- methylenecycloheptyl) palladium chloride dimer (2a) was cyclized via oxidative coupling to afford the octahydroazulene skeleton. The cyclodialkylation of 1 equiv of the dianion of dimethyl 3-ketoglutarate with 2a, followed by saponification and decarboxylation, afforded 9-ketobicyclo[5.4.0]undec-l-ene.

Comments

The Journal of Organic Chemistry, Vol. 54, No. 26 (1989): 6056-6063. DOI.

Recommended Citation

Donaldson, William; Wang, Jinkang; Cepa, Valerie G.; and Suson, John D., "Reactivity of (3-chloro-2-methylenecycloalkyl)palladium Chloride Dimers: Addition of Stabilized Carbon Nucleophiles and Application to Cyclopentannulation and Cyclohexannulation" (1989). Chemistry Faculty Research and Publications. 857.
https://epublications.marquette.edu/chem_fac/857