Synthesis of propionamide pyridine and pyridine n‐oxide ligands

Abstract

A new set of pyridine and pyridine N‐oxides functionalized with N,N‐dimethylpropionamide pendant groups in the 2‐ and 2,6‐positions have been prepared from the combination of 2‐chloromethylpyridine and 2,6‐bis(chloromethyl) pyridine with α‐lithio N,N‐dimethyl acetamide. The coordination interaction between 2‐(N,N‐dimethylpropionamide) pyridine N‐oxide (10) and Tb(NO3)3 has been unambiguously defined via single crystal X‐ray diffraction analysis of Tb(10)(NO3)3(H2O).

Iridium-Catalyzed Selective α-Alkylation of Unactivated Amides with Primary Alcohols

“…Additionally, heterocyclic alcohols, such as 2-furanmethanol ( 5k , 70%) and 2-pyridinemethanol ( 5l , 73%), underwent alkylation in useful yields. Treatment of 2,6-pyridinedimethanol with 4a afforded 2,6-bis( N , N -dimethylpropionamide)pyridine ( 5m , 53%), which is a potential liquid–liquid extractant for lanthanide and actinide metals . Alkylation of 4a with 3-phenyl-1-propanol and aliphatic alcohols such as cyclohexylmethanol, n -butanol, and n -octanol gave the corresponding N , N -dimethyl amides 5n – q in 72–83% yields.…”

Synthesis and Lanthanide Coordination Chemistry of Phosphine Oxide Decorated Dibenzothiophene and Dibenzothiophene Sulfone Platforms

“…The fundamental coordination properties of such ligands have been extensively studied, and practical applications for the ligands and their complexes are numerous. As examples, we have recently reported on the use of 2-pyridine N -oxide, [2-(X)C 5 H 4 NO], and 2,6-pyridine N -oxide, [2,6-(X) 2 C 5 H 3 NO], platforms to prepare chelating ligands decorated with functional arms X = phosphine oxide, −[P(O)R 2 ], , phosphonate, −[P(O)­(OR) 2 ], methylphosphine oxide, −[CH 2 P­(O)R 2 ], − methylphosphonate, −[CH 2 P­(O)(OR) 2 ], methylphosphinic acid, −CH 2 P­(O)(OH) 2 ], methylphosphine sulfide, −[CH 2 P(S)R 2 ], and methylamido, −[CH 2 C(O)N(H)R] and −[CH 2 CH 2 C­(O)NR 2 ] . These ligands generally favor binding with hard lanthanide cations; the 2-(X)C 5 H 4 NO compounds adopt bidentate, O N O P , , or O N O C chelate interactions, while the 2,6-(X) 2 C 5 H 3 NO compounds bond as tridentate O P O N O′ P′ − or O C O N O′ C′ chelates.…”

“…As examples, we have recently reported on the use of 2-pyridine N -oxide, [2-(X)C 5 H 4 NO], and 2,6-pyridine N -oxide, [2,6-(X) 2 C 5 H 3 NO], platforms to prepare chelating ligands decorated with functional arms X = phosphine oxide, −[P(O)R 2 ], , phosphonate, −[P(O)­(OR) 2 ], methylphosphine oxide, −[CH 2 P­(O)R 2 ], − methylphosphonate, −[CH 2 P­(O)(OR) 2 ], methylphosphinic acid, −CH 2 P­(O)(OH) 2 ], methylphosphine sulfide, −[CH 2 P(S)R 2 ], and methylamido, −[CH 2 C(O)N(H)R] and −[CH 2 CH 2 C­(O)NR 2 ] . These ligands generally favor binding with hard lanthanide cations; the 2-(X)C 5 H 4 NO compounds adopt bidentate, O N O P , , or O N O C chelate interactions, while the 2,6-(X) 2 C 5 H 3 NO compounds bond as tridentate O P O N O′ P′ − or O C O N O′ C′ chelates. In turn, favorable solubility and binding/release thermodynamic and kinetic features for several of the O P O N O′ P′ -class ligands and complexes support interesting solvent extraction performance for trivalent f-block element cations in acidic aqueous solutions. − …”

“…The fundamental coordination properties of such ligands have been extensively studied, and practical applications for the ligands and their complexes are numerous. As examples, we have recently reported on the use of 2-pyridine N-oxide, 17 These ligands generally favor binding with hard lanthanide cations; the 2-(X)C 5 H 4 NO compounds adopt bidentate, O N O P , 4,13 or O N O C 17 chelate interactions, while the 2,6-(X) 2 C 5 H 3 NO compounds bond as tridentate O P O N O′ P′ 11−17 or O C O N O′ C′ chelates. In turn, favorable solubility and binding/release thermodynamic and kinetic features for several of the O P O N O′ P′ -class ligands and complexes support interesting solvent extraction performance for trivalent f-block element cations in acidic aqueous solutions.…”

Oxidation Reactivity Channels for 2-(Pyridin-2-yl)-N,N-diphenylacetamides

“…Representative target ligands include acetamido and propionamido functionalized pyridine and pyridine N -oxide platforms. In that regard, we have recently reported the syntheses and coordination chemistry for examples of G − L . , These results have stimulated efforts to prepare the N , N -diorganyl acetamide analogues of C − F . Herein we report the syntheses and oxidation chemistry of the “one-armed” derivatives M .…”