Ruthenium-Catalyzed Asymmetric N-Acyl Nitrene Transfer Reaction: Imidation of Sulfide.,Organic Letters

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Ruthenium-Catalyzed Asymmetric N-Acyl Nitrene Transfer Reaction: Imidation of Sulfide.
Organic Letters ( IF 4.9 ) Pub Date : 2020-05-01 , DOI: 10.1021/acs.orglett.0c01373
Masaki Yoshitake ₁ , Hiroki Hayashi ₂ , Tatsuya Uchida _{2,

3}

Affiliation

The asymmetric nitrene transfer reaction is a useful and strong tool for the construction of nitrogen functional groups such as N-sulfonyl amide and carbamic ester in a highly enantioselective manner. On the other hand, there is a substantial limitation in this filed: the transfer of N-acyl amide via the corresponding nitrene intermediates is still difficult because N-acyl nitrenes undergo undesired nitrene dimerization or Curtius rearrangement. Herein, we achieved highly enantioselective imidation of sulfides via catalytic N-acyl nitrene transfer with (OC)ruthenium-salen complex 2b as the catalyst and 3-substituted 1,4,2-dioxazol-5-ones 1 as the nitrene source. Complex 2b can decompose dioxazolones 1 to the desired N-acyl nitrene intermediates without any activation via heating or UV irradiation, or transfer generating nitrene intermediates to the sulfur atom of sulfides with good to excellent enantioselectivities (≤98% ee) without diazene and isocyanate contamination.

中文翻译：

钌催化的不对称N-酰基丁二烯转移反应：酰亚胺化的硫化物。

不对称腈转移反应是用于以高度对映选择性的方式构建氮官能团（例如N-磺酰基酰胺和氨基甲酸酯）的有用且强大的工具。另一方面，该领域存在很大的局限性：通过相应的腈中间体进行N-酰基酰胺的转移仍然是困难的，因为N-酰基腈经过不希望的腈二聚或Curtius重排。在本文中，我们通过催化的N-酰基腈转移反应，以（OC）钌-沙仑络合物2b为催化剂，3-取代的1,4,2-二恶唑-5-酮1为腈源，实现了硫化物的高度对映选择性酰亚胺化。配合物2b可以将二恶唑酮1分解为所需的N-酰基腈中间体，而无需通过加热或UV辐射进行任何活化，

更新日期：2020-05-01

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