Ruthenium Pybox-Catalyzed Enantioselective Intramolecular C–H Amination of Sulfamoyl Azides en Route to Chiral Vicinal Diamines,The Journal of Organic Chemistry

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Ruthenium Pybox-Catalyzed Enantioselective Intramolecular C–H Amination of Sulfamoyl Azides en Route to Chiral Vicinal Diamines
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2020-11-25 , DOI: 10.1021/acs.joc.0c02279
Xin Nie ₁ , Zihan Yan ₁ , Sergei Ivlev ₁ , Eric Meggers ₁

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Enantioselective C(sp³)–H aminations allow an efficient access to nonracemic chiral amines. This work reports the catalytic asymmetric synthesis of chiral 1,2,5-thiadiazolidine-1,1-dioxides by an enantioselective ring-closing 1,5-C–H amination of sulfamoyl azides. The reaction is catalyzed by a recently introduced simple chiral ruthenium bis(oxazoline) (pybox) complex ( Angew. Chem. Int. Ed. 2020, 59, 12395) and provides cyclic 5-membered sulfamide products in up to 98% yield and up to 98% ee if the C–H bond is in a benzylic position. Mechanistic experiments support a stepwise mechanism in which an intermediate ruthenium nitrenoid species initiates a 1,5-hydrogen atom transfer followed by an immediate radical rebound. The cyclic sulfamide products are suitable intermediates for the synthesis of chiral vicinal diamines as has been verified for a representative example.

中文翻译：

钌磺胺催化的氨磺酰叠氮化物在手性邻二胺中的对映选择性分子内CH反应

对映选择性的C（sp ³）–H胺可有效地获得非外消旋手性胺。这项工作报告了通过氨磺酰氨基叠氮化物的对映选择性闭环1，5-CH胺催化的手性1,2,5-噻二唑烷-1,1-二氧化物的催化不对称合成。该反应通过一个最近推出的简单的手性钌双（恶唑啉）（pybox）配合物（催化的Angew。化学式中间体版 2020，59（12395）并以高达98％的收率和高达98％ee的价格提供环状5元磺酰胺产物（如果C–H键位于苄基位置）。力学实验支持逐步机制，其中中间的钌亚硝烯类物质引发1，5-氢原子转移，然后立即发生自由基反弹。环状磺酰胺产物是用于合成手性邻二胺的合适中间体，已为代表性实例证实。

更新日期：2021-01-01

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