Mechanistic Insights into the PdII‐Catalyzed Chemoselective N‐Demethylation vs. Cyclometalation Reactivity Pathways in 1‐Aryl‐N,N‐dimethylethanamines

@article{Yap2014MechanisticII,
  title={Mechanistic Insights into the PdII‐Catalyzed Chemoselective N‐Demethylation vs. Cyclometalation Reactivity Pathways in 1‐Aryl‐N,N‐dimethylethanamines},
  author={Jeanette See Leng Yap and Yi Ding and Xiang-Yuan Yang and Jonathan Wong and Yongxin Li and Sumod Appukuttan Pullarkat and Pak-Hing Leung},
  journal={European Journal of Inorganic Chemistry},
  year={2014},
  volume={2014},
  pages={5046-5052}
}
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… Expand
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References

SHOWING 1-10 OF 48 REFERENCES
Synthesis of a Chiral Palladacycle and Its Application in Asymmetric Hydrophosphanation Reactions
A novel amine ligand, 1-(2,5-dimethylphenyl)-N,N,2,2-tetramethylpropan-1-amine, was synthesized in six steps from commercially available p-xylene. Direct ortho-palladation of this amine ligandExpand
Development of a novel chiral palladacycle and its application in asymmetric hydrophosphination reaction.
TLDR
The enantiomerically pure palladacycle was used to promote the asymmetric hydrophosphination reaction between diphenylphosphine and dimethyl acetylenedicarboxylate and the (31)P{(1)H} NMR spectroscopy indicated that only one stereo-isomeric product was formed. Expand
Dinuclear Palladacyclic Complexes Derived from C−N Cleavage of an Imidazolium Salt: Synthesis, Structural Characterization, and Their Uses for C−C Coupling
Cleavage of a C−N bond of 3,6-(N-n-butylimidazolidenyl)pyridazine salt in its reactions with Ag2O and Pd(OAc)2 was observed. Subsequent palladation of the resultant N-n-butylimidazole resulted in theExpand
A rational approach to the design and synthesis of chiral organopalladium-amine complexes.
TLDR
Compared to its naphthylamine analogue, the orthopalladated 2,5-dimethylbenzylamine complex exhibits a significantly higher stereoselectivity in the chiral template promoted asymmetric cycloaddition reaction between DMPP and ethyl vinyl ketone. Expand
Design, Synthesis, and Stereochemical Evaluation of a Novel Chiral Amine–Palladacycle
A novel chiral palladacycle containing ortho-metallated (±)-1-(3,6-dimethylnaphthalen-2-yl)-N,N-dimethylethylaminewas designed and synthesized by a multi-step synthesis by usingExpand
Synthesis of a stereochemically defined 1,2-diazetine N,N'-dioxide and a study of its thermal decomposition.
TLDR
The stereospecific formation of trans-stilbene suggests a mechanism of decomposition in which C-N bond cleavage leads to a diradical intermediate stabilized by the phenyl group. Expand
Synthesis of 2,3-disubstituted benzofurans and indoles by π-Lewis acidic transition metal-catalyzed cyclization of ortho-alkynylphenyl O,O- and N,O-acetals
Abstract The PtCl2-catalyzed cyclization reaction of ortho-alkynylphenyl acetals 1 in the presence of COD (1,5-cyclooctadiene) produces 3-(α-alkoxyalkyl)benzofurans 2 in good to high yields. ForExpand
Rational Design of a Novel Chiral Palladacycle: Synthesis, Optical Resolution, and Stereochemical Evaluation
A novel palladacycle Was designed and prepared by direct cyclopalladation of the ligand 1-(3,6-dimethylnaphthalen-1-yl)-N,N-dimethylethanamine, which was synthesized by a multistep sequence startingExpand
Palladium-catalyzed dynamic kinetic asymmetric transformations of vinyl aziridines with nitrogen heterocycles: rapid access to biologically active pyrroles and indoles.
TLDR
It is reported that nitrogen heterocycles can serve as competent nucleophiles in the palladium-catalyzed dynamic kinetic asymmetric alkylation of vinyl aziridines with high regio-, chemo- and enantioselectivity. Expand
Synthesis, Coordination Characteristics, Conformational Behavior, and Bond Reactivity Studies of a Novel Chiral Phosphapalladacycle Complex
A novel five-membered dimeric phosphapalladacycle was prepared using palladium(II) acetate as the ortho-palladation source. A successful optical resolution of the palladacycle was achieved throughExpand
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