Biaryl Phosphine Based Pd(II) Amido Complexes: The Effect of Ligand Structure on Reductive Elimination
Kinetic studies conducted under both catalytic and stoichiometric conditions were employed to investigate the reductive elimination of RuPhos (2-dicyclohexylphosphino-2′,6′-diisopropoxybiphenyl) based palladium amido complexes. These complexes were found to be the resting state in Pd-catalyzed cross...
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American Chemical Society (ACS)
2018
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| Online Access: | http://hdl.handle.net/1721.1/113057 https://orcid.org/0000-0003-1523-411X https://orcid.org/0000-0003-3875-4775 |
| _version_ | 1811078992974839808 |
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| author | Arrechea, Pedro L Buchwald, Stephen Leffler |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Arrechea, Pedro L Buchwald, Stephen Leffler |
| author_sort | Arrechea, Pedro L |
| collection | MIT |
| description | Kinetic studies conducted under both catalytic and stoichiometric conditions were employed to investigate the reductive elimination of RuPhos (2-dicyclohexylphosphino-2′,6′-diisopropoxybiphenyl) based palladium amido complexes. These complexes were found to be the resting state in Pd-catalyzed cross-coupling reactions for a range of aryl halides and diarylamines. Hammett plots demonstrated that Pd(II) amido complexes derived from electron-deficient aryl halides or electron-rich diarylamines undergo faster rates of reductive elimination. A Hammett study employing SPhos (2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl) and analogues of SPhos demonstrated that electron donation of the lower aryl group is key to the stability of the amido complex with respect to reductive elimination. The rate of reductive elimination of an amido complex based on a BrettPhos-RuPhos hybrid ligand (2-(dicyclohexylphosphino)-3,6-dimethoxy-2′,6′-diisopropoxybiphenyl) demonstrated that the presence of the 3-methoxy substituent on the "upper" ring of the ligand slows the rate of reductive elimination. These studies indicate that reductive elimination occurs readily for more nucleophilic amines such as N-alkyl anilines, N,N-dialkyl amines, and primary aliphatic amines using this class of ligands. |
| first_indexed | 2024-09-23T11:08:28Z |
| format | Article |
| id | mit-1721.1/113057 |
| institution | Massachusetts Institute of Technology |
| last_indexed | 2024-09-23T11:08:28Z |
| publishDate | 2018 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1130572022-10-01T01:33:47Z Biaryl Phosphine Based Pd(II) Amido Complexes: The Effect of Ligand Structure on Reductive Elimination Arrechea, Pedro L Buchwald, Stephen Leffler Massachusetts Institute of Technology. Department of Chemistry Arrechea, Pedro L Buchwald, Stephen Leffler Kinetic studies conducted under both catalytic and stoichiometric conditions were employed to investigate the reductive elimination of RuPhos (2-dicyclohexylphosphino-2′,6′-diisopropoxybiphenyl) based palladium amido complexes. These complexes were found to be the resting state in Pd-catalyzed cross-coupling reactions for a range of aryl halides and diarylamines. Hammett plots demonstrated that Pd(II) amido complexes derived from electron-deficient aryl halides or electron-rich diarylamines undergo faster rates of reductive elimination. A Hammett study employing SPhos (2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl) and analogues of SPhos demonstrated that electron donation of the lower aryl group is key to the stability of the amido complex with respect to reductive elimination. The rate of reductive elimination of an amido complex based on a BrettPhos-RuPhos hybrid ligand (2-(dicyclohexylphosphino)-3,6-dimethoxy-2′,6′-diisopropoxybiphenyl) demonstrated that the presence of the 3-methoxy substituent on the "upper" ring of the ligand slows the rate of reductive elimination. These studies indicate that reductive elimination occurs readily for more nucleophilic amines such as N-alkyl anilines, N,N-dialkyl amines, and primary aliphatic amines using this class of ligands. National Institutes of Health (U.S.) (Award GM058160) National Institutes of Health (U.S.) (Award 3-R01-GM058160-14S1) 2018-01-10T21:21:13Z 2018-01-10T21:21:13Z 2016-08 2016-06 2018-01-10T15:34:54Z Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/113057 Arrechea, Pedro Luis, and Buchwald, Stephen L. “Biaryl Phosphine Based Pd(II) Amido Complexes: The Effect of Ligand Structure on Reductive Elimination.” Journal of the American Chemical Society 138, 38 (September 2016): 12486–12493 © 2016 American Chemical Society https://orcid.org/0000-0003-1523-411X https://orcid.org/0000-0003-3875-4775 http://dx.doi.org/10.1021/JACS.6B05990 Journal of the American Chemical Society Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) ACS |
| spellingShingle | Arrechea, Pedro L Buchwald, Stephen Leffler Biaryl Phosphine Based Pd(II) Amido Complexes: The Effect of Ligand Structure on Reductive Elimination |
| title | Biaryl Phosphine Based Pd(II) Amido Complexes: The Effect of Ligand Structure on Reductive Elimination |
| title_full | Biaryl Phosphine Based Pd(II) Amido Complexes: The Effect of Ligand Structure on Reductive Elimination |
| title_fullStr | Biaryl Phosphine Based Pd(II) Amido Complexes: The Effect of Ligand Structure on Reductive Elimination |
| title_full_unstemmed | Biaryl Phosphine Based Pd(II) Amido Complexes: The Effect of Ligand Structure on Reductive Elimination |
| title_short | Biaryl Phosphine Based Pd(II) Amido Complexes: The Effect of Ligand Structure on Reductive Elimination |
| title_sort | biaryl phosphine based pd ii amido complexes the effect of ligand structure on reductive elimination |
| url | http://hdl.handle.net/1721.1/113057 https://orcid.org/0000-0003-1523-411X https://orcid.org/0000-0003-3875-4775 |
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