Stereodivergent Allylation of Azaaryl Acetamides and Acetates by Synergistic Iridium and Copper Catalysis.
Stereodivergent Allylation of Azaaryl Acetamides and Acetates by Synergistic Iridium and Copper Catalysis.
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DOI：
10.1021/jacs.7b12824
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发表时间：
2018-01-31
影响因子：
15
通讯作者：
Hartwig JF
中科院分区：
文献类型：
--
作者：
Jiang X;Boehm P;Hartwig JF
我们报道了烯丙基酯与氮杂芳基乙酰胺和乙酸酯衍生的前手性烯醇化物的立体分散烯丙基取代反应，以形成烯丙基部分与两种催化剂，手性金属环铱络合物和手性双膦连接的铜（I）络合物，分别单独控制亲电和亲核碳原子的构型加成的烯醇化物的产物。通过对两种催化剂的对映体进行简单的置换，分别合成了含有两个立体中心的产物的所有四种立体异构体，具有高的非对映体选择性和对映体选择性。发现带有吡啶基、苯并噻唑基、苯并恶唑基、吡嗪基、喹啉基和异喹啉基部分的各种氮杂芳基乙酰胺和乙酸酯都适合于这种转化。
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.
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影响因子：
8.4
作者：
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通讯作者：
Macmillan DW
影响因子：
5.2
作者：
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