A Stereoselective Approach to (Z)-1-Silyl-2-aryl-1,3-dienes from 4-(Phenylselanyl)but-1-yne via Palladium-Catalyzed Silylstannylation and Selenoxide Elimination

Abstract

The palladium-catalyzed silylstannylation of 4-(phenylselanyl)but-1-yne proceeded regio-and stereoselectively, followed by selenoxide elimination via oxidation to give (Z)-1-(trimethylsilyl)-2-(tributylstannyl)buta-1,3-diene in good yield. This conjugated diene underwent the Stille coupling reaction with various aryl iodides in the presence of Pd(PPh 3 ) 4 to afford (Z)-2-aryl-1-(trimethylsilyl)buta-1,3-dienes with high stereoselectivity. Reversing the order of selenoxide elimination and Stille coupling reaction in the synthetic procedure also resulted in good yields of (Z)-2-aryl-1-(trimethylsilyl)buta-1,3-dienes.

Boron and Silicon-Substituted 1,3-Dienes and Dienophiles and Their Use in Diels-Alder Reactions

“…Segi and co-workers reported a simple method for stereoselective synthesis of ( Z )-1-silyl-2-aryl-1,3-dienes ( 115 ) ( Scheme 30 ) [ 29 ]. This method used palladium-catalyzed silylstannylation of 4-(phenylselenyl)-but-1-yne ( 113 ) followed by oxidation-selenoxide elimination and Stille coupling.…”

“…The authors found that once the initial silylstannylation was completed the oxidation-selenoxide elimination and Stille coupling could be performed in either sequence with essentially identical overall yields for the sequence. Segi and co-workers reported a simple method for stereoselective synthesis of (Z)-1-silyl-2-aryl-1,3-dienes (115) (Scheme 30) [29]. This method used palladium-catalyzed silylstannylation of 4-(phenylselenyl)-but-1-yne (113) followed by oxidation-selenoxide elimination and Stille coupling.…”