Catalyst Choice for Highly Enantioselective [3 + 3]-Cycloaddition of Enoldiazocarbonyl Compounds
Catalyst Choice for Highly Enantioselective [3 + 3]-Cycloaddition of Enoldiazocarbonyl Compounds
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DOI：
10.1021/acscatal.8b03391
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发表时间：
2018-09
期刊：
影响因子：
12.9
通讯作者：
Kostiantyn O. Marichev;Frady G. Adly;Alejandra M. Carranco;Estevan C Garcia;H. Arman;M. Doyle
中科院分区：
文献类型：
--
作者：
Kostiantyn O. Marichev;Frady G. Adly;Alejandra M. Carranco;Estevan C Garcia;H. Arman;M. Doyle
手性铜(I)催化剂优于手性二钠（II）催化剂，用于烯醛基二氮羰基化合物与硝基和酰基吡啶类化合物的[3 + 3]-环加成反应，生成手性恶嗪和吡嗪，收率和对映选择性非常高。烯内二氮酮的反应产率和立体选择性与相应的酯和酰胺的反应产率和立体选择性几乎相同，但烯内二氮酮的产物是手性1,3-二羰基衍生物的前体，通过形成吡唑和异恶唑，为杂环合成提供了额外的机会。
Chiral copper(I) catalysts are preferred over chiral dirhodium(II) catalysts for [3 + 3]-cycloaddition reactions of enoldiazocarbonyl compounds with nitrones and acyliminopyridinium ylides, forming chiral oxazines and pyrazines in very high yield and enantioselectivity. Yields and stereoselectivities from reactions of enoldiazoketones are virtually the same as those from the corresponding esters and amides, but products from enoldiazoketones are precursors to chiral 1,3-dicarbonyl derivatives that provide additional opportunities in heterocyclic synthesis through the formation of pyrazoles and isoxazoles.