Intramolecular C(sp3 )-H Bond Oxygenation by Transition-Metal Acylnitrenoids.,Angewandte Chemie International Edition

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Intramolecular C(sp3 )-H Bond Oxygenation by Transition-Metal Acylnitrenoids.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-07-30 , DOI: 10.1002/anie.202009335
Yuqi Tan ₁ , Shuming Chen ₂ , Zijun Zhou ₁ , Yubiao Hong ₁ , Sergei Ivlev ₁ , K N Houk ₂ , Eric Meggers ₁

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This study demonstrates for the first time that easily accessible transition‐metal acylnitrenoids can be used for controlled direct C(sp³)‐H oxygenations. Specifically, a ruthenium catalyst activates N‐benzoyloxycarbamates as nitrene precursors towards regioselective intramolecular C−H oxygenations to provide cyclic carbonates, hydroxylated carbamates, or 1,2‐diols. The method can be applied to the chemoselective C−H oxygenation of benzylic, allylic, and propargylic C(sp³)−H bonds. The reaction can be performed in an enantioselective fashion and switched in a catalyst‐controlled fashion between C−H oxygenation and C−H amination. This work provides a new reaction mode for the regiocontrolled and stereocontrolled conversion of C(sp³)‐H into C(sp³)−O bonds.

中文翻译：

分子内C（sp3）-H键氧合过渡金属酰基类肾上腺素。

这项研究首次证明了易于获得的过渡金属酰基类肾上腺素可用于受控的C（sp ³）-H直接氧化。具体而言，钌催化剂将N-苯甲酰氧基氨基甲酸酯作为氮烯前体活化，以进行区域选择性的分子内CH氧化，从而提供环状碳酸酯，羟基化的氨基甲酸酯或1,2-二醇。该方法可应用于苄基，烯丙基和炔丙基C（sp ³）-H键的化学选择性CH氧化。该反应可以以对映选择性的方式进行，并可以在CH氧化和CH胺化之间以催化剂控制的方式切换。这项工作提供了用于C（SP的regiocontrolled和立体控制转换新的反应模式³）-H成C（SP ³）-O键。

更新日期：2020-07-30

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