Journal of the American Chemical Society p. 6036 - 6050 (2020)
Update date:2022-08-03
Topics:
Budiman, Yudha P.
Friedrich, Alexandra
Jayaraman, Arumugam
Kerner, Florian
Marder, Todd B.
Radius, Udo
C-C reductive elimination from [PdL2(C6F5)2] to form polyfluorinated biaryls has been a challenge for over 50 years. Thus, palladium-catalyzed homocoupling of arylboronates (ArF-Bpin) containing two ortho-fluorine substituents is very difficult, as the reaction typically stops at the [PdL2(ArF)2] stage after two transmetalation steps. The transmetalated complexes cis-[Pd(MeCN)2(C6F5)2] (3a), cis-[Pd(MeCN)2(2,4,6-C6F3H2)2] (3b), and cis-[Pd(MeCN)2(2,6-C6F2H3)2] (3e) have been isolated from the reaction of ArF-Bpin with Pd(OAc)2 in acetonitrile solvent, with no homocoupling observed. However, catalytic homocoupling proceeds smoothly in a "weakly coordinating" arene solvent as long as no ancillary ligands or coordinating solvents are present. DFT computations reveal that the active catalyst formed by arene solvent coordination leads to an overall reduced barrier for the reductive elimination step compared to the formation of stable [PdL2(ArF)2] complexes in the presence of a donor ligand or solvent L.
View MoreJiaxing Taixin Pharmaceutical Chemical Co., Ltd
Contact:0573-82613601
Address:Chemical Park, Jiaxing, Zhejiang, China
HANGZHOU TOYOND BIOTECH CO., LTD
Contact:+86-571-86965177
Address:No. 189, Fengqi East Road, Hangzhou, China
Suqian Ruixing Chemical Co., Ltd.
Contact:+86-527-80805666(总机);84836008(销售)
Address:3 Jingsilu, Zone north, Hubin Xincheng Development Park, Suqian, China
Sinoway International (Jiangsu) Co., Ltd.
Contact:+86-25-86630167
Address:17 Beijing Road (West), Nanjing, China
Shanghai Haoyuan Chemexpress Co., Ltd.
website:https://www.chemexpress.com/
Contact:86-21-58950125
Address:No.3 Building, No.1999, Zhangheng Road, ZhangjiangHighTech Park, Shanghai, P.R.China,201203
Doi:10.1016/j.bmc.2007.08.046
(2007)Doi:10.1016/j.tetasy.2006.08.013
(2006)Doi:10.1002/ps.2780410305
(1994)Doi:10.1021/ja064481j
(2006)Doi:10.1016/S0957-4166(00)00043-4
(2000)Doi:10.1080/00397910600764212
(2006)