Direct asymmetric Michael reactions of cyclic 1,3-dicarbonyl compounds and enamines catalyzed by chiral bisoxazoline-copper(II) complexes
Direct asymmetric Michael reactions of cyclic 1,3-dicarbonyl compounds and enamines catalyzed by chiral bisoxazoline-copper(II) complexes
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DOI：
10.1021/jo0343026
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发表时间：
2003-06-27
影响因子：
3.6
通讯作者：
Jorgensen, KA
中科院分区：
文献类型：
--
作者：
Halland, N;Velgaard, T;Jorgensen, KA
研究了环状1，3-二羰基化合物与烯胺对不饱和2-酮酯的直接Michael加成反应。一系列不同的4-羟基香豆素、4-羟基-6-甲基-2-吡喃酮、3-羟基-1H-非那烯-1-酮、2-羟基-1，4-萘醌、5，5-二甲基-1，3-环己二酮和环状1，3-二酮的各种烯胺都以对映选择性方式加成到不饱和4-取代2-酮酯上。该反应由手性双恶唑啉-铜（II）配合物催化，在无碱条件下进行，以良好至高产率提供Michael加合物，ee高达98%。所形成的产物是重要生物和药物分子骨架中的子结构。讨论了新反应的应用范围和潜力，并对催化不对称反应的机理进行了探讨。
The catalytic direct Michael addition of cyclic 1,3-dicarbonyl compounds and enamines to unsaturated 2-ketoesters is presented. A series of different 4-hydroxycoumarins, 4-hydroxy-6-methyl-2-pyrone, 3-hydroxy- 1H-phenalene-1-one, 2-hydroxy-1,4-naphthoquinone, 5,5-dimethyl-1,3-cyclohexanedione, and various enamines of cyclic 1,3-diketones all add to unsaturated 4-substituted 2-ketoesters in an enantioselective manner. The reaction is catalyzed by chiral bisoxazoline-copper(II) complexes and proceeds in the absence of base to afford Michael adducts in good to high yields and with up to 98% ee. The products formed are substructures found in skeletons of important biological and pharmaceutical molecules. The scope and potential of the new reaction are discussed as well as the mechanism for the catalytic enantioselective reaction.