Reaction pathway of conjugate addition of lithium organozincates to s-trans-enones

Masanobu Uchiyama; Shinji Nakamura; Taniyuki Furuyama; Eiichi Nakamura; Keiji Morokuma

doi:10.1021/ja070123k

Reaction pathway of conjugate addition of lithium organozincates to s-trans-enones

Masanobu Uchiyama, Shinji Nakamura, Taniyuki Furuyama, Eiichi Nakamura, Keiji Morokuma

SCI - Chemistry

Research output: Contribution to journal › Article › peer-review

16 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	13360-13361
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	129
Issue number	44
DOIs	https://doi.org/10.1021/ja070123k
Publication status	Published - 2007 Nov 7

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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abstract = "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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AU - Uchiyama, Masanobu

AU - Nakamura, Shinji

AU - Furuyama, Taniyuki

AU - Nakamura, Eiichi

AU - Morokuma, Keiji

PY - 2007/11/7

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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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Reaction pathway of conjugate addition of lithium organozincates to s-trans-enones

Abstract

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