Cargando…

A rational pre-catalyst design for bis-phosphine mono-oxide palladium catalyzed reactions

Significant catalyst loading reduction and increased reaction robustness have been achieved for a Pd-catalyzed asymmetric intramolecular C–N coupling through comprehensive mechanistic studies. Detailed kinetic, spectroscopic, and crystallographic analyses revealed that the mono-oxidation of the bis-...

Descripción completa

Detalles Bibliográficos
Autores principales: Ji, Yining, Li, Hongming, Hyde, Alan M., Chen, Qinghao, Belyk, Kevin M., Lexa, Katrina W., Yin, Jingjun, Sherer, Edward C., Williamson, R. Thomas, Brunskill, Andrew, Ren, Sumei, Campeau, Louis-Charles, Davies, Ian W., Ruck, Rebecca T.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2017
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5427683/
https://www.ncbi.nlm.nih.gov/pubmed/28553522
http://dx.doi.org/10.1039/c6sc05472b
_version_ 1783235676304572416
author Ji, Yining
Li, Hongming
Hyde, Alan M.
Chen, Qinghao
Belyk, Kevin M.
Lexa, Katrina W.
Yin, Jingjun
Sherer, Edward C.
Williamson, R. Thomas
Brunskill, Andrew
Ren, Sumei
Campeau, Louis-Charles
Davies, Ian W.
Ruck, Rebecca T.
author_facet Ji, Yining
Li, Hongming
Hyde, Alan M.
Chen, Qinghao
Belyk, Kevin M.
Lexa, Katrina W.
Yin, Jingjun
Sherer, Edward C.
Williamson, R. Thomas
Brunskill, Andrew
Ren, Sumei
Campeau, Louis-Charles
Davies, Ian W.
Ruck, Rebecca T.
author_sort Ji, Yining
collection PubMed
description Significant catalyst loading reduction and increased reaction robustness have been achieved for a Pd-catalyzed asymmetric intramolecular C–N coupling through comprehensive mechanistic studies. Detailed kinetic, spectroscopic, and crystallographic analyses revealed that the mono-oxidation of the bis-phosphine ligand is critical for a successful transformation. (31)P NMR studies provided an understanding of the inefficient activation of the Pd(OAc)(2)/(R,R)-QuinoxP* pre-catalyst to form the active bis-phosphine mono-oxide–Pd(0) catalyst with competitive formation of a less active (R,R)-QuinoxP*·PdBr(2) complex. Based on these detailed mechanistic studies, a new series of bis-phosphine mono-oxides (BPMO)-ligated Pd(ii) pre-catalysts have been rationally developed that allow for reliable and complete catalyst activation which should have general utility in academic and industrial settings.
format Online
Article
Text
id pubmed-5427683
institution National Center for Biotechnology Information
language English
publishDate 2017
publisher Royal Society of Chemistry
record_format MEDLINE/PubMed
spelling pubmed-54276832017-05-26 A rational pre-catalyst design for bis-phosphine mono-oxide palladium catalyzed reactions Ji, Yining Li, Hongming Hyde, Alan M. Chen, Qinghao Belyk, Kevin M. Lexa, Katrina W. Yin, Jingjun Sherer, Edward C. Williamson, R. Thomas Brunskill, Andrew Ren, Sumei Campeau, Louis-Charles Davies, Ian W. Ruck, Rebecca T. Chem Sci Chemistry Significant catalyst loading reduction and increased reaction robustness have been achieved for a Pd-catalyzed asymmetric intramolecular C–N coupling through comprehensive mechanistic studies. Detailed kinetic, spectroscopic, and crystallographic analyses revealed that the mono-oxidation of the bis-phosphine ligand is critical for a successful transformation. (31)P NMR studies provided an understanding of the inefficient activation of the Pd(OAc)(2)/(R,R)-QuinoxP* pre-catalyst to form the active bis-phosphine mono-oxide–Pd(0) catalyst with competitive formation of a less active (R,R)-QuinoxP*·PdBr(2) complex. Based on these detailed mechanistic studies, a new series of bis-phosphine mono-oxides (BPMO)-ligated Pd(ii) pre-catalysts have been rationally developed that allow for reliable and complete catalyst activation which should have general utility in academic and industrial settings. Royal Society of Chemistry 2017-04-01 2017-01-19 /pmc/articles/PMC5427683/ /pubmed/28553522 http://dx.doi.org/10.1039/c6sc05472b Text en This journal is © The Royal Society of Chemistry 2017 https://creativecommons.org/licenses/by/3.0/This is an Open Access article distributed under the terms of the Creative Commons Attribution 3.0 Unported License (http://creativecommons.org/licenses/by/3.0/ (https://creativecommons.org/licenses/by/3.0/) ) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
spellingShingle Chemistry
Ji, Yining
Li, Hongming
Hyde, Alan M.
Chen, Qinghao
Belyk, Kevin M.
Lexa, Katrina W.
Yin, Jingjun
Sherer, Edward C.
Williamson, R. Thomas
Brunskill, Andrew
Ren, Sumei
Campeau, Louis-Charles
Davies, Ian W.
Ruck, Rebecca T.
A rational pre-catalyst design for bis-phosphine mono-oxide palladium catalyzed reactions
title A rational pre-catalyst design for bis-phosphine mono-oxide palladium catalyzed reactions
title_full A rational pre-catalyst design for bis-phosphine mono-oxide palladium catalyzed reactions
title_fullStr A rational pre-catalyst design for bis-phosphine mono-oxide palladium catalyzed reactions
title_full_unstemmed A rational pre-catalyst design for bis-phosphine mono-oxide palladium catalyzed reactions
title_short A rational pre-catalyst design for bis-phosphine mono-oxide palladium catalyzed reactions
title_sort rational pre-catalyst design for bis-phosphine mono-oxide palladium catalyzed reactions
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5427683/
https://www.ncbi.nlm.nih.gov/pubmed/28553522
http://dx.doi.org/10.1039/c6sc05472b
work_keys_str_mv AT jiyining arationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions
AT lihongming arationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions
AT hydealanm arationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions
AT chenqinghao arationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions
AT belykkevinm arationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions
AT lexakatrinaw arationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions
AT yinjingjun arationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions
AT shereredwardc arationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions
AT williamsonrthomas arationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions
AT brunskillandrew arationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions
AT rensumei arationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions
AT campeaulouischarles arationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions
AT daviesianw arationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions
AT ruckrebeccat arationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions
AT jiyining rationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions
AT lihongming rationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions
AT hydealanm rationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions
AT chenqinghao rationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions
AT belykkevinm rationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions
AT lexakatrinaw rationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions
AT yinjingjun rationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions
AT shereredwardc rationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions
AT williamsonrthomas rationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions
AT brunskillandrew rationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions
AT rensumei rationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions
AT campeaulouischarles rationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions
AT daviesianw rationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions
AT ruckrebeccat rationalprecatalystdesignforbisphosphinemonooxidepalladiumcatalyzedreactions