Palladium(0)-catalyzed cyclization of electron-deficient enynes and enediynes

Yoshihiko Yamamoto; Shoji Kuwabara; Yoji Ando; Hitomi Nagata; Hisao Nishiyama; Kenji Itoh

doi:10.1021/jo049072p

Palladium(0)-catalyzed cyclization of electron-deficient enynes and enediynes

J Org Chem. 2004 Oct 1;69(20):6697-705. doi: 10.1021/jo049072p.

Authors

Yoshihiko Yamamoto¹, Shoji Kuwabara, Yoji Ando, Hitomi Nagata, Hisao Nishiyama, Kenji Itoh

Affiliation

¹ Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa, Nagoya 464-8603, Japan. yamamoto@apchem.nagoya-u.ac.jp

PMID: 15387592
DOI: 10.1021/jo049072p

Abstract

In the presence of a Pd(0) precatalyst, Pd2(bq)2(nbe)2 or Pd2(dba)3, 1,6-enyne esters were heated in refluxing benzene to give cyclodimers as single regioisomers. On the other hand, the combination of the Pd(0) precatalyst and triphenyl phosphite gave rise to various cycloisomerization products depending on the substitution pattern of the enyne esters. Six-membered ring cycloisomerization products were predominantly obtained from enyne esters bearing methallyl or 2-phenyl-2-propenyl moieties, while other enyne esters afforded normal five-membered ring cycloisomerization products. Intramolecular [2 + 2 + 2] cyclocotrimerization of enediyne esters also proceeded in the presence of the Pd(0) precatalyst and triphenylphosphine to give fused cyclohexadienes.