Journal of Organic Chemistry p. 4179 - 4190 (2019)
Update date:2022-08-03
Topics:
Xue, Jing-Wen
Zeng, Miao
Zhang, Sicheng
Chen, Zhuqi
Yin, Guochuan
Exploring new catalysts for efficient organic synthesis is among the most attractive topics in chemistry. Here, using Ni(OAc)2/LA as catalyst (LA: Lewis acid), a novel catalyst strategy was developed for oxidative coupling of thiols and phosphonates to phosphorothioates with oxygen oxidant. The present study discloses that when Ni(OAc)2 alone was employed as the catalyst, the reaction proceeded very sluggishly with low yield, whereas adding non-redox-active metal ions such as Y3+ to Ni(OAc)2 dramatically promoted its catalytic efficiency. The promotional effect is highly Lewis acidity dependent on the added Lewis acid, and generally, a stronger Lewis acid provided a better promotional effect. The stopped-flow kinetics confirmed that adding Y(OTf)3 can obviously accelerate the activation of thiols by Ni(II) and next accelerate its reaction with phosphonate to generate the phosphorothioate product. ESI-MS characterizations of the catalyst disclosed the formation of the heterobimetallic Ni(II)/Y(III) species in the catalyst solution. Additionally, this Ni(II)/LA catalyst can be applied in the synthesis of a series of phosphorothioate compounds including several commercial bioactive compounds. This catalyst strategy has clearly supported that Lewis acid can significantly improve the catalytic efficiency of these traditional metal ions in organic synthesis, thus opening up new opportunities in their catalyst design.
View Morewebsite:http://www.lonwinchem.com
Contact:Tel: 86-21-59858395
Address:No#966,Huaxu Road,Shanghai 201702,P.R.China
ANHUI CHEM-BRIGHT BIOENGINEERING CO.,LTD
Contact:86-561-4080321
Address:No.8 Lieshan Industrial Zone of Huaibei
Changzhou Medi-tech Bioscientific Co., Ltd.
Contact:86-519-83246372
Address:Number 115 Menghedadao Road, Changzhou, Jiangsu, China
Hangzhou Showland Technology Co., Ltd.
Contact:86-571-88920516
Address:ROOM2118,NO.553,WENSAN ROAD,HANGZHOU,CHINA
Shandong Jusage Technology Co.,Ltd.
Contact:86-13406130167
Address:No.20,North Ride No.9 Road, Guangrao Economic Development Zone, Shandong Province
Doi:10.1021/jo00082a011
(1994)Doi:10.1134/S1070428013120166
()Doi:10.1021/acs.orglett.6b03131
(2016)Doi:10.1021/jo4024705
(2014)Doi:10.1021/om4007032
(2014)Doi:10.1021/ja00075a008
(1993)