Mechanistic insights into the PdII-catalyzed chemoselective N-demethylation vs. cyclometalation reactivity pathways in 1-Aryl-N,N-dimethylethanamines
Two structurally isomeric substituted N,N-dimethylethanamines have been prepared. Treatment of the 2,4-di-tert-butylphenyl isomer with PdII ions generated the ortho-metalated complexes. On the other hand, treatment of the 2,5-di-tert-butylphenyl-substituted amine resulted in the unexpected chemosele...
| Main Authors: | , , , , , , |
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| Format: | Journal Article |
| Language: | English |
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2014
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| Online Access: | https://hdl.handle.net/10356/105314 http://hdl.handle.net/10220/20485 http://dx.doi.org/10.1002/ejic.201402547 |
| _version_ | 1826121241335955456 |
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| author | Yap, Jeanette See Leng Ding, Yi Yang, Xiang-Yuan Wong, Jonathan Li, Yongxin Pullarkat, Sumod A. Leung, Pak-Hing |
| author2 | School of Physical and Mathematical Sciences |
| author_facet | School of Physical and Mathematical Sciences Yap, Jeanette See Leng Ding, Yi Yang, Xiang-Yuan Wong, Jonathan Li, Yongxin Pullarkat, Sumod A. Leung, Pak-Hing |
| author_sort | Yap, Jeanette See Leng |
| collection | NTU |
| description | Two structurally isomeric substituted N,N-dimethylethanamines have been prepared. Treatment of the 2,4-di-tert-butylphenyl isomer with PdII ions generated the ortho-metalated complexes. On the other hand, treatment of the 2,5-di-tert-butylphenyl-substituted amine resulted in the unexpected chemoselective cleavage of one of the three N–C bonds, thus generating the corresponding secondary amine. The N-demethylation process could be catalyzed at room temperature by palladium(II) catalysts such as PdCl2 or Pd(OAc)2. Furthermore, treatment with a stoichiometric amount of PdII ions gave a metal complex in which both secondary amines were bound to Pd in an N-monodentate fashion. When triethylamine was introduced, one of the N-ethyl groups in NEt3 was cleaved, and an unexpected heteroamine complex was produced. The products generated were isolated and characterized by X-ray crystallography. Mechanistic insights into the cyclometalation and C–N cleavage observed are discussed. |
| first_indexed | 2024-10-01T05:29:10Z |
| format | Journal Article |
| id | ntu-10356/105314 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T05:29:10Z |
| publishDate | 2014 |
| record_format | dspace |
| spelling | ntu-10356/1053142019-12-06T21:49:04Z Mechanistic insights into the PdII-catalyzed chemoselective N-demethylation vs. cyclometalation reactivity pathways in 1-Aryl-N,N-dimethylethanamines Yap, Jeanette See Leng Ding, Yi Yang, Xiang-Yuan Wong, Jonathan Li, Yongxin Pullarkat, Sumod A. Leung, Pak-Hing School of Physical and Mathematical Sciences DRNTU::Science::Chemistry::Inorganic chemistry Two structurally isomeric substituted N,N-dimethylethanamines have been prepared. Treatment of the 2,4-di-tert-butylphenyl isomer with PdII ions generated the ortho-metalated complexes. On the other hand, treatment of the 2,5-di-tert-butylphenyl-substituted amine resulted in the unexpected chemoselective cleavage of one of the three N–C bonds, thus generating the corresponding secondary amine. The N-demethylation process could be catalyzed at room temperature by palladium(II) catalysts such as PdCl2 or Pd(OAc)2. Furthermore, treatment with a stoichiometric amount of PdII ions gave a metal complex in which both secondary amines were bound to Pd in an N-monodentate fashion. When triethylamine was introduced, one of the N-ethyl groups in NEt3 was cleaved, and an unexpected heteroamine complex was produced. The products generated were isolated and characterized by X-ray crystallography. Mechanistic insights into the cyclometalation and C–N cleavage observed are discussed. 2014-09-10T06:26:22Z 2019-12-06T21:49:04Z 2014-09-10T06:26:22Z 2019-12-06T21:49:04Z 2014 2014 Journal Article Yap, J. S. L., Ding, Y., Yang, X. Y., Wong, J., Li, Y., Pullarkat, S. A., & Leung, P. H. (2014). Mechanistic Insights into the Pd II -Catalyzed Chemoselective N -Demethylation vs. Cyclometalation Reactivity Pathways in 1-Aryl- N , N -dimethylethanamines . European Journal of Inorganic Chemistry, 2014(29), 5046-5052. 1434-1948 https://hdl.handle.net/10356/105314 http://hdl.handle.net/10220/20485 http://dx.doi.org/10.1002/ejic.201402547 en European journal of inorganic chemistry © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. |
| spellingShingle | DRNTU::Science::Chemistry::Inorganic chemistry Yap, Jeanette See Leng Ding, Yi Yang, Xiang-Yuan Wong, Jonathan Li, Yongxin Pullarkat, Sumod A. Leung, Pak-Hing Mechanistic insights into the PdII-catalyzed chemoselective N-demethylation vs. cyclometalation reactivity pathways in 1-Aryl-N,N-dimethylethanamines |
| title | Mechanistic insights into the PdII-catalyzed chemoselective N-demethylation vs. cyclometalation reactivity pathways in 1-Aryl-N,N-dimethylethanamines |
| title_full | Mechanistic insights into the PdII-catalyzed chemoselective N-demethylation vs. cyclometalation reactivity pathways in 1-Aryl-N,N-dimethylethanamines |
| title_fullStr | Mechanistic insights into the PdII-catalyzed chemoselective N-demethylation vs. cyclometalation reactivity pathways in 1-Aryl-N,N-dimethylethanamines |
| title_full_unstemmed | Mechanistic insights into the PdII-catalyzed chemoselective N-demethylation vs. cyclometalation reactivity pathways in 1-Aryl-N,N-dimethylethanamines |
| title_short | Mechanistic insights into the PdII-catalyzed chemoselective N-demethylation vs. cyclometalation reactivity pathways in 1-Aryl-N,N-dimethylethanamines |
| title_sort | mechanistic insights into the pdii catalyzed chemoselective n demethylation vs cyclometalation reactivity pathways in 1 aryl n n dimethylethanamines |
| topic | DRNTU::Science::Chemistry::Inorganic chemistry |
| url | https://hdl.handle.net/10356/105314 http://hdl.handle.net/10220/20485 http://dx.doi.org/10.1002/ejic.201402547 |
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