Development of Novel Asymmetric Reactions Based on Acid-base Catalysis of Late Transition Metal Complexes
Development of Novel Asymmetric Reactions Based on Acid-base Catalysis of Late Transition Metal Complexes
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基于后过渡金属配合物酸碱催化的新型不对称反应的进展
DOI：
10.5059/yukigoseikyokaishi.69.972
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发表时间：
2011
影响因子：
0.2
通讯作者：
M. Sodeoka
中科院分区：
文献类型：
--
作者：
Y. Hamashima;M. Sodeoka
描述了具有硬阴离子配体如羟基和乙酸配体的手性过渡金属配合物的酸碱催化作用。Pd、Pt、Cu和Ni配合物可以在非碱性条件下有效地萃取亚甲基和甲基化合物的α-质子，得到手性烯醇化物。在1,3-二羰基化合物的情况下，Pd配合物即使在酸性条件下也能产生这种烯醇化物，它们与质子酸的协同作用可以激活各种亲电试剂，包括烯酮、亚胺和缩醛，从而使独特的C-C键形成反应具有优异的对映选择性。此外，不对称质子化在aza-Michael反应中使用Pd羟基配合物与胺盐的组合进行了描述。为了有效激活酸性较弱的α-酮酯，我们开发了一种新的手性醋酸镍配合物，它特别有效地促进了对硝基烯烃的不对称共轭加成。为了证实该反应的实用性，成功地将其应用于不对称合成MFPA。最后，简要讨论了这些反应的反应机理。
Acid-base catalysis of chiral transition metal complexes having hard anionic ligands such as hydroxo and acetate ligands is described. The Pd, Pt, Cu, and Ni complexes can effectively abstract the α-proton of methylene and methine compounds under non-basic conditions to give chiral enolates. In the case of 1,3-dicarbonyl compounds, the Pd complexes produced such enolates even under acidic conditions, and their cooperative action with protic acid to activate the various electrophiles including enones, imines, and acetals allows unique C-C bond-forming reactions to proceed with excellent enantioselectivity. Additionally, asymmetric protonation in aza-Michael reaction using the Pd hydroxo complex in combination with amine salt is described. For efficient activation of less acidic α-ketoesters, we developed a novel chiral nickel acetate complex, which is particularly effective to promote the asymmetric conjugate addition to nitroolefins. To confirm the utility of the reaction, its application to the asymmetric synthesis of MFPA was successfully demonstrated. Finally, the proposed reaction mechanisms of these reactions are briefly discussed.
影响因子：
15
作者：
Evans, DA;Seidel, D;Downey, CW
通讯作者：
Downey, CW
影响因子：
16.6
作者：
Taylor, MS;Tokunaga, N;Jacobsen, EN
通讯作者：
Jacobsen, EN
影响因子：
46.2
作者：
Trost BM;Brindle CS
通讯作者：
Brindle CS