Cyclization/Hydrosilylation of Functionalized Dienes Catalyzed by a Cationic Palladium Phenanthroline Complex

Mixtures of (phen)PdMe 2 ( 2a ) and HBAr‘ 4 ( 3a ) or (phen)PdMe(Cl) ( 2b ) and NaBAr‘ 4 ( 3b ) [phen = 1,10-phenanthroline; Ar‘ = 3,5-C 6 H 3 (CF 3 ) 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.