Journal of Organometallic Chemistry p. 89 - 95 (1997)
Update date:2022-08-05
Topics:
Brunner, Henri
Bluechel, Christian
Doyle, Michael P.
The copper-catalyzed Meerwein reaction of activated olefins with arenediazonium halides leads to a formal addition of aryl halide to the olefinic double bond. Methyl acrylate, p-tolyldiazonium tetrafluoroborate and tetrabutylammonium chloride in anhydrous acetonitrile were used as a model system, the product being methyl a-chloro-β-tolylpropionate. Applying a newly established methodology, the isolated diazonium tetrafluoroborate and an equivalent amount of tetrabutylammonium chloride were added to the olefin and the copper catalyst, containing optically active ligands, such as 2-and 2,6-pyridinyloxazolines and bisoxazolines. The low optical inductions obtained in the room temperature reaction could be raised to 8.7% ee in the low temperature variant at -40 °C. Two phenyl substituents in the neighborhood of the chiral centers in the bisoxazoline ligands of the catalyst and increasing steric bulk in the ester group of the substrate (methyl, ethyl, menthyl) increase the stereoselectivity of the Meerwein arylation. Replacement of the p-tolyldiazonium salt by the mesityldiazonium salt caused the optical induction in the formation of the corresponding mesityl product rise to 19.5% ee. Thus, though considered to be a radical reaction, the Meerwein arylation of activated olefins can be rendered enantioselective by using copper catalysts with optically active ligands.
View MoreJiande City Silibase Silicone New Material Manufacture Co., Ltd.
Contact:15967177856
Address:Genglou Industrial Development Area
Zibo Jujin Chemical Industry Co., Ltd.(Dongming Jujin Chemical Industry Co., Ltd. )
Contact:+86-533-2975022
Address:No.99 Shanquan Road, Zhangdian District
Shandong Jusage Technology Co.,Ltd.
Contact:86-13406130167
Address:No.20,North Ride No.9 Road, Guangrao Economic Development Zone, Shandong Province
Wuxi Morality Chemical Co., Ltd
Contact:
Address:B/7F, 321th WuYun Rd, Wanda Plaza, Wuxi City, 214174, China
Shijiazhuang Haotian Chemical Co., Ltd.
Contact:86-311-85044374
Address:293 Donggang Road
Doi:10.1002/cbic.201200315
(2012)Doi:10.1002/zaac.19744030203
(1974)Doi:10.1021/acs.macromol.5b00496
(2015)Doi:10.1016/S0040-4039(00)96681-4
(1987)Doi:10.1021/jo00932a017
(1974)Doi:10.1016/j.tetlet.2005.09.032
(2005)