Synthesis, optical resolution, and stereochemical properties of a rationally designed chiral C–N palladacycle

  title={Synthesis, optical resolution, and stereochemical properties of a rationally designed chiral C–N palladacycle},
  author={Jeanette See Leng Yap and Houguang Jeremy Chen and Yongxin Li and Sumod Appukuttan Pullarkat and Pak-Hing Leung},
A novel racemic tertiary amine, 1-(2,5-diisopropylphenyl)-N,N-dimethylethanamine, was synthesized from 2,5-diisopropylbenzaldehyde via a multistep approach in high overall yield. The ortho palladation of this ligand was found to be sensitive to the reaction conditions and the palladating reagents employed. The metal complexation process could thus generate a cyclopalladated complex in high yield, lead to an unexpected N-demethylated amine palladium(II) complex, or both. Both products have been… Expand
6 Citations
Determination of the Absolute Configuration of CN-Palladacycles by 31P{1H} NMR Spectroscopy using (1R,2S,5R)-Menthyloxydiphenylphosphine as the Chiral Derivatizing Agent: Efficient Chirality Transfer in Phosphinite Adducts
A series of (1R)-MenOPPh2 phosphinite derivatives of α-arylalkylaminate CN-palladacycles of known absolute configuration was prepared. Their structure and stereochemistry were determined usingExpand
Synthesis of a novel six membered CNS palladacycle; TD-DFT study and catalytic activity towards microwave-assisted selective oxidation of terminal olefin to aldehyde
Abstract This article documented synthesis of a Schiff base, E-2-(benzylthio)- N -{(2-methoxynaphthalene-1-yl)methylene}benzenamine (HL) by the treatment of 2-meyhoxynaphthaldehyde andExpand
Enantiopurity determination of CN-palladacycles using 31P NMR spectroscopy with (1R,2S,5R)-menthyloxydiphenylphosphine as chiral derivatizing agent
Abstract The known readily available phosphinite, (1 R ,2 S ,5 R )-menthyloxydiphenylphosphine, was introduced as a chiral derivatizing agent for the enantiomeric purity determination of theExpand
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


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
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 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
Synthesis and the Stereoelectronic Properties of Novel Cyclopalladated Complexes Derived from Enantiomerically Pure (R/S)-N,N-Dimethyl- 1-(9-phenanthryl)ethylamine
A series of enantiomerically pure organopalladium complexes containing the resolved ortho-metalated (R/S)-N,N-dimethyl-1-(9-phenanthryl)ethylamine ligand have been prepared. The absolute ringExpand
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
Novel Synthesis of Chiral 1,3-Diphosphines via Palladium Template Promoted Hydrophosphination and Functional Group Transformation Reactions
A novel cyano-functionalized monophosphine palladium substrate containing the ortho-metalated (R)-(1-(dimethylamino)ethyl)naphthalene as the chiral auxiliary was synthesized fromExpand
Asymmetric synthesis of a chiral hetero-bidentate As–P ligand containing both As and P-stereogenic centres
Abstract The organopalladium complex containing ortho-metalated ( S )-[1-(dimethylamino)ethyl]naphthalene as the chiral auxiliary has been used as the chiral template to promote the asymmetricExpand
A planar chiral non-metallocenic analogue of the most popular N,N-dimethylbenzylaminate palladacycle
Abstract A racemic planar chiral tertiary amine pCp-CH2NMe2 (HL1, pCp = [2.2]paracyclophane-4-yl) was prepared by aminomethylation of the bromide pCp-Br with Eschenmoser’s salt. DirectExpand
Asymmetric synthesis of diphosphine ligands containing phosphorus and carbon stereogenic centers by means of a chiral palladium complex promoted hydrophosphination reaction.
An organopalladium complex containing ortho-metalated (R)-(1-(dimethylamino) ethyl)naphthalene as the chiral auxiliary has been used to promote the asymmetric hydrophosphination reaction betweenExpand
Synthesis and resolution of an α-phenyl substituted ortho -palladated matrix
Abstract A novel ortho -palladated benzylaminate matrix bearing phenyl substituent at the α-carbon stereocenter was prepared in the racemic state by direct intramolecular palladation of tertiaryExpand