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},
  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},
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
4 Citations
Palladium-Catalyzed Oxidative N-Dealkylation/Carbonylation of Tertiary Amines with Alkynes to α,β-Alkynylamides.
The first highly effective Pd/C-catalyzed oxidative N-dealkylation/carbonylation of various aliphatic as well as cyclic tertiary amines with alkynes has been described. The selective sp(3) C-N bondExpand
Challenges in cyclometalation: steric effects leading to competing pathways and η1,η2-cyclometalated iridium(iii) complexes.
The iridation of (R)-N,N-dimethyl-1-(1-naphthyl)ethylamine in the presence of a base afforded an assortment of products ranging from organic molecules to coordinated systems and cyclometalated complexes, and generated an unprecedented carbocyclic η1,η2-cycloiridated species that could not be attained from the directcyclometalation of its organic ligand. Expand
Transition-Metal-Catalyzed Cleavage of C-N Single Bonds.
This paper presents the results of aalysis experiments conducted at the BNLMS and Nankai University with real-time measurements of the response of the H2O-O2/O2 mixture to E2O/O3 mixture. Expand


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.
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.
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.
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.
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