TY - JOUR
T1 - 1,4-Addition of Bis(iodozincio)methane to α,β-Unsaturated ketones
T2 - Chemical and theoretical/computational studies
AU - Sada, Mutsumi
AU - Furayama, Taniyuki
AU - Komagawa, Shinsuke
AU - Uchiyama, Masanobu
AU - Matsubara, Seijiro
PY - 2010/9/10
Y1 - 2010/9/10
N2 - 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.
AB - 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.
KW - Addition reactions
KW - Density functional calculations domino reactions
KW - Ketones
KW - Tandem reactions
KW - Zinc
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U2 - 10.1002/chem.201000738
DO - 10.1002/chem.201000738
M3 - Article
C2 - 20645344
AN - SCOPUS:77956420961
VL - 16
SP - 10474
EP - 10481
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 34
ER -