ACS Catalysis p. 1793 - 1798 (2016)
Update date:2022-08-03
Topics:
Fasano, Valerio
Radcliffe, James E.
Ingleson, Michael J.
In contrast to the established dogma that B(C6F5)3 is irreversibly poisoned by excess H2O/amine (or imine) bases, B(C6F5)3 is actually a water-tolerant catalyst for the reductive amination of primary and secondary arylamines with aldehydes and ketones in "wet solvents" at raised temperatures and using only 1.2 equiv of Me2PhSiH as reductant. Arylamines/N-arylimines do not result in the irreversible deprotonation of H2O-B(C6F5)3, allowing sufficient B(C6F5)3 to be evolved at raised temperatures to effect catalytic reductions. Stronger Br?nsted basic amines such as tBuNH2 (and derived imines) result in irreversible formation of [HO-B(C6F5)3]- from H2O-B(C6F5)3, precluding the formation of B(C6F5)3 at raised temperatures and thus preventing any imine reduction. A substrate scope exploration using 1 mol % nonpurified B(C6F5)3 and "wet solvents" demonstrates that this is an operationally simple and effective methodology for the production of secondary and tertiary arylamines in high yield, with imine reduction proceeding in preference to other possible reactions catalyzed by B(C6F5)3, including the dehydrosilylation of H2O and the reduction of carbonyl moieties (e.g., esters).
View MoreTianjin Bright Future Technology Co., Ltd
Contact:0086-22-58016666
Address:NO.136 DongTeng Lake Street Tianjin Economic and Technology Development Area,Tainjin,China
Zhejiang Chemline International Co., Ltd.
Contact:+86-571-88062298
Address:Hengdian Industry Area, Dongyang, Zhejiang, China
website:http://www.joyochem.com
Contact:0531-82687558, 0531-82687326
Address:Factory Building 11, Jinan Comprehensive free trade zone, Shandong, China
Nanjing Chemical Material Corp.(NCMC)
website:http://www.njchemm.com
Contact:0086-25-83172879
Address:B12 Technology and Innovation Building, Nanjing Tech University, No.5 New Model Road
Jiacheng-Chem Enterprises Limited
Contact:86-571-86711508
Address:19 Floor, CIBC Holley International Building, No. 198,Wuxing Road, Hangzhou, China,310020
Doi:10.1021/jm00053a017
(1993)Doi:10.1002/anie.201101941
(2011)Doi:10.1002/asia.201100190
(2011)Doi:10.1002/ejoc.201601604
(2017)Doi:10.1002/cphc.201000943
(2011)Doi:10.1039/c39900001544
(1990)