Efficient Catalytic Enantioselective Hydroxyamination of α-Aryl-α-Cyanoacetates with 2-Nitrosopyridines.
Efficient Catalytic Enantioselective Hydroxyamination of α-Aryl-α-Cyanoacetates with 2-Nitrosopyridines.
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DOI：
10.1002/chem.201800592
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发表时间：
2018-03
期刊：
影响因子：
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通讯作者：
Jingchuan Zhang;K. Fu;Lili Lin;Yan Lu;Xiaohua Liu;Xiaoming Feng
中科院分区：
文献类型：
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作者：
Jingchuan Zhang;K. Fu;Lili Lin;Yan Lu;Xiaohua Liu;Xiaoming Feng
以手性N，N '-二氧化物/Mg（OTf）2为催化剂，实现了α-芳基-α-氰基乙酸酯与2-亚硝基吡啶的高对映选择性完全N-选择性羟胺化反应，丰富了亚硝基化学.在低至0.05mol%的催化剂负载量下，以优异的产率获得了多种具有季立体中心和潜在抗菌活性的2-氰基-2-[羟基（吡啶-2-基）氨基]乙酸酯，具有良好至优异的ee值。产物可容易地转化为有用的α-氨基酰胺和1，2-二胺。此外，提出了一个可能的过渡态模型来解释手性诱导的起源。
The highly enantioselective totally N-selective hydroxyamination reaction of α-aryl-α-cyanoacetates with 2-nitrosopyridines was realized by using a chiral N,N'-dioxide/Mg(OTf)2 complex as catalyst, which enriches the nitroso chemistry. A variety of 2-cyano-2-[hydroxyl(pyrydin-2-yl)amino]acetates with quaternary stereocenters and potential antibacterial activities were obtained in excellent yields with good to excellent ee values under as low as 0.05 mol % catalyst loading. The products could be easily transformed to useful α-amino amides and 1,2-diamines. Besides, a possible transition state model was proposed to elucidate the origin of the chirality induction.