Journal of the American Chemical Society p. 8460 - 8468 (2015)
Update date:2022-07-30
Topics:
Brusoe, Andrew T.
Hartwig, John F.
We report the synthesis of fluorinated anilines by palladium-catalyzed coupling of fluoroalkylamines with aryl bromides and aryl chlorides. The products of these reactions are valuable because anilines typically require the presence of an electron-withdrawing substituent on nitrogen to suppress aerobic or metabolic oxidation, and the fluoroalkyl groups have steric properties and polarity distinct from those of more common electron-withdrawing amide and sulfonamide units. The fluoroalkylaniline products are unstable under typical conditions for C-N coupling reactions (heat and strong base). However, the reactions conducted with the weaker base KOPh, which has rarely been used in cross-coupling to form C-N bonds, occurred in high yield in the presence of a catalyst derived from commercially available AdBippyPhos and [Pd(allyl)Cl]2. Under these conditions, the reactions occur with low catalyst loadings (<0.50 mol % for most substrates) and tolerate the presence of various functional groups that react with the strong bases that are typically used in Pd-catalyzed C-N cross-coupling reactions of aryl halides. The resting state of the catalyst is the phenoxide complex, (BippyPhosPd(Ar)OPh); due to the electron-withdrawing property of the fluoroalkyl substituent, the turnover-limiting step of the reaction is reductive elimination to form the C-N bond.
View MoreNINGBO YINLIANG FOREIGN TRADE CO., LTD.
Contact:+86-574-87834016 / 87898057
Address:23F NO.666JINYU ROAD,YINGZHOU DISTRICT,NINGBO.CHINA
Shandong Zhongcheng Barium Salt Co., Ltd
Contact:+86-15725732638
Address:No.29 baoxi road, hi-tech zone, zibo, shandong
website:http://www.alwaychem.com
Contact:+86-532-8586-4000, 8586-5000
Address:NO.51, TAIPING ROAD, QINGDAO, CHINA. 266001
China Synchem Technology Co.,Ltd
website:http://www.cnsynchem.com
Contact:+86-0552-4929311
Address:No.217 Daqing Road
WUHU HUAHAI BIOLOGY ENGINEERING CO LTD
Contact:+86-553-3836920
Address:7/F NO.82 LAODONG ROAD WUHU CHINA
Doi:10.1021/jm980454v
(1999)Doi:10.1016/S0040-4039(01)80455-X
(1989)Doi:10.1080/15257779908041625
(1999)Doi:10.1021/jm00335a001
(1964)Doi:10.1055/s-1999-2752
(1999)Doi:10.1021/acs.inorgchem.9b03334
(2020)