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Title: Mechanistic insights into the PdII-catalyzed chemoselective N-demethylation vs. cyclometalation reactivity pathways in 1-Aryl-N,N-dimethylethanamines
Authors: Yap, Jeanette See Leng
Ding, Yi
Yang, Xiang-Yuan
Wong, Jonathan
Li, Yongxin
Pullarkat, Sumod A.
Leung, Pak-Hing
Keywords: DRNTU::Science::Chemistry::Inorganic chemistry
Issue Date: 2014
Source: 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.
Series/Report no.: European journal of inorganic chemistry
Abstract: 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.
ISSN: 1434-1948
DOI: 10.1002/ejic.201402547
Rights: © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Fulltext Permission: none
Fulltext Availability: No Fulltext
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