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Selective Difunctionalization of Unactivated Aliphatic Alkenes Enabled by a Metal–Metallaaromatic Catalytic System
Journal of the American Chemical Society ( IF 15.0 ) Pub Date : 2022-01-25 , DOI: 10.1021/jacs.1c12586
Fei-Hu Cui 1 , Yuhui Hua 1, 2 , Yu-Mei Lin 1 , Jiawei Fei 1 , Le-Han Gao 1 , Xiaodan Zhao 3 , Haiping Xia 1, 2
Affiliation  

The design of organometallic catalysts is crucial in the development of catalytic reactions. Herein, we describe a heterometallic [Os-Cu] complex with the characteristics of bimetallics, metallaaromatics, and pincer complexes. This complex serves as a highly effective catalyst for selective amino- and oxyselenation of unactivated alkenes. More than 80 examples including challenging substrates of unsymmetric aliphatic alkenes and amine-based nucleophiles in such reactions are provided. These reactions produce 1,2-difunctionalized products with good yields and high levels of chemo-, regio-, and stereoselectivity. Our studies revealed the following: (i) The usually inert osmium center activates the N- or O-centered nucleophiles. (ii) The copper–osmium bonding and its cooperative effects play essential roles in control the selectivity by bringing the reaction components into close proximity. (iii) The metallaaromatic moiety helps to stabilize the intermediate. These findings provide a versatile platform for catalyst design based on metal–metallaaromatic cooperative effects that have not been attained previously with bimetallic complexes.

中文翻译:

金属-金属芳烃催化体系对未活化脂肪烯烃的选择性双官能化

有机金属催化剂的设计对于催化反应的发展至关重要。在此,我们描述了一种具有双金属、金属芳烃和钳形配合物特征的异金属[Os-Cu]配合物。该配合物可作为一种高效催化剂,用于未活化烯烃的选择性氨基和氧硒化。提供了 80 多个示例,包括此类反应中具有挑战性的不对称脂肪族烯烃和胺基亲核试剂的底物。这些反应产生具有良好收率和高水平化学、区域和立体选择性的 1,2-双官能化产物。我们的研究揭示了以下内容:(i)通常惰性的锇中心激活N - 或O- 中心的亲核试剂。(ii) 铜-锇键及其协同效应通过使反应组分靠近,在控制选择性方面发挥着重要作用。(iii) 金属芳族部分有助于稳定中间体。这些发现为基于金属-金属芳烃协同效应的催化剂设计提供了一个多功能平台,这是以前用双金属配合物无法实现的。
更新日期:2022-02-09
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