Ru
<sup>V</sup>
‐Acylimido Intermediate in [Ru
<sup>IV</sup>
(Por)Cl
<sub>2</sub>
]‐Catalyzed C–N Bond Formation: Spectroscopic Characterization, Reactivity, and Catalytic Reactions
作者:Dan‐Yan Hong、Yungen Liu、Liangliang Wu、Vanessa Kar‐Yan Lo、Patrick H. Toy、Siu‐Man Law、Jie‐Sheng Huang、Chi‐Ming Che
DOI:10.1002/anie.202100668
日期:2021.8.16
bond formation reactions via acylnitrene transfer have recently attracted much attention, but direct detection of the proposed acylnitrenoid/acylimido M(NCOR) (R=aryl or alkyl) species in these reactions poses a formidable challenge. Herein, we report on Ru(NCOR) intermediates in C−N bond formation catalyzed by [RuIV(Por)Cl2]/N3COR, a catalytic method applicable to aziridine/oxazoline formation from
通过酰基硝烯转移的金属催化的 CN 键形成反应最近引起了很多关注,但在这些反应中直接检测所提出的酰基硝烯/酰基酰亚胺 M(NCOR)(R = 芳基或烷基)物质是一项艰巨的挑战。在此,我们报告了由 [Ru IV (Por)Cl 2 ]/N 3 COR 催化形成 CN 键的 Ru(NCOR) 中间体,这是一种适用于从烯烃形成氮丙啶/恶唑啉、取代吲哚胺化、α -由甲硅烷基烯醇醚形成氨基酮,C(sp 3)−H 键,以及天然产物和碳水化合物衍生物的功能化(产率高达 99%)。实验研究,包括 HR-ESI-MS 和 EPR 测量,加上 DFT 计算,为 Ru(NCOR) 酰基硝烯类化合物作为 Ru V -imido 物种的配方提供了证据。