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Combined Experimental and Computational Study on Ruthenium(II)-Catalyzed Reactions of Diynes with Aldehydes and N,N-Dimethylformamide

Yamamoto, Yoshihiko, Okude, Yuta, Mori, Shota, Shibuya, Masatoshi
Journal of organic chemistry 2017 v.82 no.15 pp. 7964-7973
aldehydes, ambient temperature, carbon, catalysts, chemical structure, cycloaddition reactions, dimethylformamide, ketones, ligands, organic chemistry, pyrans, rhodium, ruthenium, stereoselectivity
Cycloaddition reactions of 1,6-diynes bearing methyl terminal groups with p-anisaldehyde were conducted using a cationic ruthenium catalyst with a η⁵-pentamethylcyclopentadienyl ligand in THF at room temperature to afford dienyl ketones via ring opening of the initially formed fused pyrans. (Z)-Stereoisomers of dienyl ketones were selectively obtained using the ruthenium catalyst, whereas previously reported rhodium catalysts produced (E)-isomers. These (E)- and (Z)-selectivities are kinetically controlled as the control experiments showed that the E/Z-isomerization of (E)-dienylketone occurs at 70 °C for 10 h to afford an E/Z-ratio of almost 1:1. The origin of this characteristic stereoselectivity for the ruthenium catalyst was attributed to the direct ring opening of the CpRu⁺-coordinated pyran complex intermediates on the basis of theoretical calculations [PCM (THF) M06L/SDD-6-311++G(d,p)//B3LYP/LanL2DZ-6-31G(d)] and control experiments. The (Z)-selectivity increased when the bulkiness of the diyne terminal substituents increased. Notably, the reaction of 1,6-diynes bearing tert-butyl terminal groups with various α,β-unsaturated aldehydes exclusively afforded (Z)-dienyl ketones even at 70 °C when a cationic ruthenium complex with a smaller η⁵-cyclopentadienyl (Cp) ligand was used as the catalyst. The same Cp complex was found to be also efficient for the hydrocarbamoylative cyclization of sterically demanding 1,6-diynes bearing tertiary or quaternary carbon tethers with N,N-dimethylformamide.