Stereodivergent Allylation of Azaaryl Acetamides and Acetates by Synergistic Iridium and Copper Catalysis,Journal of the American Chemical Society

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Stereodivergent Allylation of Azaaryl Acetamides and Acetates by Synergistic Iridium and Copper Catalysis
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2018-01-17 , DOI: 10.1021/jacs.7b12824
Xingyu Jiang ₁ , Philip Boehm ₁ , John F Hartwig ₁

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We report stereodivergent allylic substitution reactions of allylic esters with prochiral enolates derived from azaaryl acetamides and acetates to form products from addition of the enolates at the most substituted carbon of an allyl moiety with two catalysts, a chiral metallacyclic iridium complex and a chiral bisphosphine-ligated copper(I) complex, which individually control the configuration of the electrophilic and nucleophilic carbon atoms, respectively. By simple permutations of enantiomers of the two catalysts, all four stereoisomers of products containing two stereogenic centers were synthesized individually with high diastereoselectivity and enantioselectivity. A variety of azaaryl acetamides and acetates bearing pyridyl, benzothiazolyl, benzoxazolyl, pyrazinyl, quinolinyl and isoquinolinyl moieties were all found to be suitable for this transformation.

中文翻译：

铱和铜的协同催化实现氮杂芳基乙酰胺和乙酸酯的立体发散烯丙基化

我们报道了烯丙酯与衍生自氮杂芳基乙酰胺和乙酸酯的前手性烯醇化物的立体发散烯丙基取代反应，通过使用两种催化剂（手性金属环铱络合物和手性双膦配位物）在烯丙基部分取代最多的碳上加成烯醇化物而形成产物铜(I)配合物，分别单独控制亲电子和亲核碳原子的构型。通过两种催化剂对映异构体的简单排列，分别合成了含有两个立构中心的产物的所有四种立体异构体，具有高非对映选择性和对映选择性。多种带有吡啶基、苯并噻唑基、苯并恶唑基、吡嗪基、喹啉基和异喹啉基部分的氮杂芳基乙酰胺和乙酸酯都被发现适合于这种转化。

更新日期：2018-01-17

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