Cyclization/hydrosilylation of functionalized dienes catalyzed by a cationic palladium phenanthroline complex

Journal Article (Journal Article)

Mixtures of (phen)PdMe2 (2a) and HBAr'4 (3a) or (phen)PdMe(Cl) (2b) and NaBAr'4 (3b) [phen = 1,10-phenanthroline; Ar' = 3,5-C6H3(CF3)2] catalyzed the cyclization/hydrosilylation of functionalized 1,6-dienes to form silylated cyclopentanes in good yield and with excellent trans selectivity about the newly formed C-C bond (typically > 50:1). A range of tertiary hydrosilanes were employed in the procedure although unhindered trialkylsilanes provided the most consistent results. The protocol tolerated a range of polar functionality including esters, ethers, amides, sulfones, and cyano groups. 4,4-Disubstitution on the diene backbone promoted cyclization, and a homoallylic ester, ketone, or ether directing group was required for efficient cyclization. The procedure tolerated dienes which possessed a single trans-substituted olefin and also tolerated allylic substitution. These substituted dienes underwent cyclization/hydrosilylation to form carbocycles resulting from transfer of the silyl group to the less hindered olefin. Mixtures of 2a and 3a also catalyzed the cyclization/hydrosilylation of functionalized 1,7-dienes to form silylated cyclohexane derivatives. Cyclization/hydrosilylation of 1,7-dienes was typically slower, less stereoselective, and more sensitive to substitution than was cyclization of 1,6-dienes.

Full Text

Duke Authors

Cited Authors

  • Widenhoefer, RA; Stengone, CN

Published Date

  • November 12, 1999

Published In

Volume / Issue

  • 64 / 23

Start / End Page

  • 8681 - 8692

International Standard Serial Number (ISSN)

  • 0022-3263

Digital Object Identifier (DOI)

  • 10.1021/jo9913006

Citation Source

  • Scopus