1204698-79-2Relevant academic research and scientific papers
A tandem reaction initiated by 1,4-addition of bis(iodozincio)methane for 1,3-diketone formation
Sada, Mutsumi,Matsubara, Seijiro
, p. 432 - 433 (2010)
(Chemical Equation Presented) Treatment of an γ-acyloxy-α, β-unsaturated ketone with bis(iodozincio)methane leads to a novel tandem reaction consisting of three steps: (1) 1,4-addition of the dizinc reagent to the enone, which affords the corresponding zinc enolate of the β-zinciomethylated ketone; (2) intramolecular nucleophilic attack by the enolate on the ester group; and (3) Grob-type fragmentation of the adduct, accompanied by elimination of the zinc alkoxide of allyl alcohol. The overall reaction gives 1,3-diketones efficiently. Copyright
1,4-Addition of Bis(iodozincio)methane to α,β-Unsaturated ketones: Chemical and theoretical/computational studies
Sada, Mutsumi,Furayama, Taniyuki,Komagawa, Shinsuke,Uchiyama, Masanobu,Matsubara, Seijiro
experimental part, p. 10474 - 10481 (2010/10/21)
1,4-Addition of bis(iodozincio)methane to simple α,β-unsaturated ketones does not proceed well; the reaction is slightly endothermic according to DFT calculations. In the presence of chlorotrimethylsilane, the reaction proceeded efficiently to afford a silyl enol ether of β-zinciomethyl ketone. The CZn bond of the silyl enol ether could be used in a cross-coupling reaction to form another C-C bond in a one-pot reaction. In contrast, 1,4-addition of the dizinc reagent to enones carrying an acyloxy group proceeded very efficiently without any additive. In this case, the product was a 1,3-diketone, which was generated in a novel tandem reaction. A theoretical/computational study indicates that the whole reaction pathway is exothermic, and that two zinc atoms of bis(iodozincio)methane accelerate each step cooperatively as effective Lewis acids.
