Selective Difunctionalization of Unactivated Aliphatic Alkenes Enabled by a Metal-Metallaaromatic Catalytic System

Cui，Fei Hu1; Hua，Yuhui1,2; Lin，Yu Mei1; Fei，Jiawei1; Gao，Le Han1; Zhao，Xiaodan3; Xia，Haiping1,2

2022-02-09

10.1021/jacs.1c12586

Journal of the American Chemical Society   影响因子和分区

0002-7863

1520-5126

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.

SCI ; EI

英语

ESI高被引 ; NI论文

通讯

National Natural Science Foundation of China[21671164];National Natural Science Foundation of China[21931002];National Natural Science Foundation of China[22071206];National Natural Science Foundation of China[92156021];

Chemistry

Chemistry, Multidisciplinary

WOS:000766221400035

AMER CHEMICAL SOC

20220611606102

Catalysis ; Catalysts ; Copper compounds ; Olefins ; Organometallics ; Osmium

Precious Metals:547.1 ; Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Organic Compounds:804.1

2-s2.0-85124164073

Scopus

1.State Key Laboratory of Physical Chemistry of Solid Surfaces,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen,Fujian,361005,China
2.Shenzhen Grubbs Institute,Department of Chemistry,Southern University of Science and Technology,Shenzhen,518055,China
3.School of Chemistry,Sun Yat-Sen University,Guangzhou,510275,China

Cui，Fei Hu,Hua，Yuhui,Lin，Yu Mei,et al. Selective Difunctionalization of Unactivated Aliphatic Alkenes Enabled by a Metal-Metallaaromatic Catalytic System[J]. Journal of the American Chemical Society,2022,144(5):2301-2310.

Cui，Fei Hu.,Hua，Yuhui.,Lin，Yu Mei.,Fei，Jiawei.,Gao，Le Han.,...&Xia，Haiping.(2022).Selective Difunctionalization of Unactivated Aliphatic Alkenes Enabled by a Metal-Metallaaromatic Catalytic System.Journal of the American Chemical Society,144(5),2301-2310.

Cui，Fei Hu,et al."Selective Difunctionalization of Unactivated Aliphatic Alkenes Enabled by a Metal-Metallaaromatic Catalytic System".Journal of the American Chemical Society 144.5(2022):2301-2310.