Nickel-catalyzed highly regio- and stereoselective three-component assembly of allenes, aryl iodides, and alkenylzirconium reagents.

Abstract

Cyclohexylallene (1a) and alkenylzirconium reagent (n-PrCH=CHZr(Cp)2Cl) undergo three-component assembly with a variety of aromatic iodides (R1-I: R1 = 4-PhOMe, 4-PhCOMe, 4-PhMe, 2-thiophene, 2-PhOMe, 3-PhOMe, and 4-PhCO2Et) in the presence of NiCl2(PPh3)2 and zinc powder in THF at 50 degrees C to afford corresponding three-component assembly products in moderate to good yields with very high regio- and stereoselectivity. In addition to cyclohexylallene, also phenylallene, n-butylallene, cyclopentylallene, and cycloheptylallene underwent the three-component assembling reaction to furnish the corresponding 1,4-diene derivatives in good yields. Several alkenylzirconium reagents (R2CH=CHZr(Cp)2Cl: R2 = Ph (3b), t-Bu, TMS) were also employed for this three-component assembly. The nickel-catalyzed three-component assembly was further extended to vinyl iodides. Thus, 1a reacts with 3b and ethyl (Z)-3-iodoacrylate to produce a highly substituted triene in excellent yield. In all of these three-component assembly reactions, the E isomers were formed predominantly with E/Z ratios between 94/6 and 99/1. A possible mechanism for this highly regio- and stereoselective three-component assembly is proposed.