TY - JOUR
T1 - Reaction pathway of conjugate addition of lithium organozincates to s-trans-enones
AU - Uchiyama, Masanobu
AU - Nakamura, Shinji
AU - Furuyama, Taniyuki
AU - Nakamura, Eiichi
AU - Morokuma, Keiji
PY - 2007/11/7
Y1 - 2007/11/7
N2 - Density functional theory (DFT) calculations were performed to understand the reaction mechanism of organozincates in 1,4-addition to methyl vinyl ketone (MVK). Examination of the addition of Me3ZnLi to MVK as compared with that of (MeLi)2 showed that the precise transition state structures critically determine the reaction selectivity for α,β-unsaturated carbonyl compounds. In the case of organozincates, the 1,4-addition proceeds smoothly through an open form TS, whereas alkyllithiums favor 1,2-addition through a closed TS. This 1,4-addition mechanism of Zn-ates does not involve an electron transfer process and is different from the reaction of organocuprates, in which oxidation/reduction of the copper atom occurs.
AB - Density functional theory (DFT) calculations were performed to understand the reaction mechanism of organozincates in 1,4-addition to methyl vinyl ketone (MVK). Examination of the addition of Me3ZnLi to MVK as compared with that of (MeLi)2 showed that the precise transition state structures critically determine the reaction selectivity for α,β-unsaturated carbonyl compounds. In the case of organozincates, the 1,4-addition proceeds smoothly through an open form TS, whereas alkyllithiums favor 1,2-addition through a closed TS. This 1,4-addition mechanism of Zn-ates does not involve an electron transfer process and is different from the reaction of organocuprates, in which oxidation/reduction of the copper atom occurs.
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U2 - 10.1021/ja070123k
DO - 10.1021/ja070123k
M3 - Article
C2 - 17941634
AN - SCOPUS:35948973877
VL - 129
SP - 13360
EP - 13361
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 44
ER -