Wydział Chemii

Anna Skarżyńska

Anna Pyra

Marta Kowalczyk

2024

Applied Organometallic Chemistry

38

e7336/1-e7336/18

10.1002/aoc.7336

Naukowa

Angielski

Artykuł

Several platinum (II) complexes bearing heteroatom-substituted phosphine oxides ligand H(O)P(OCMe₂CMe₂O) were obtained. The H-phosphonate was synthesized in an alternative, one-pot procedure with the use of water from hexamethylphosphorus triamide and pinacol. In the presence of H(O)P (OCMe₂CMe₂O) ligand, [PtCl₂(cod)] was converted into three new complexes: [PtCl₂{P(OH)(OCMe₂CMe₂O)}₂] [Pt1], [PtCl{P(O)(OCMe₂CMe₂O)}{P(OH)(OCMe₂CMe₂O)}₂] [Pt2], and [Pt{P(OH)(OCMe₂CMe₂O)}₄]Cl₂ [Pt3]. When [PtCl₂(PPh₃)₂] was utilized as the substrate, [PtCl(PPh₃)₂{P(OH)(OCMe₂CMe₂O)}]Cl [Pt4] and [PtCl(PPh₃)₂{P(O)(OCMe₂CMe₂O)}] [Pt5] complexes were obtained, as the results of reaction with H(O)P(OCMe₂CMe₂O) and HP(OCMe₂CMe₂O)(OCH₂CMe₂NH) ligands. The structural features of all complexes were characterized by physicochemical and spectroscopic methods as well as single X-ray diffraction studies. Complex [Pt1] was found to promote cascade reaction, the addition of water to triple bond, and hydrogen/deuterium exchange reaction. The hydration reaction of substituted terminal aryl alkynes gave exclusively Markovnikov products and tolerated different functional groups. Various aryl ketones were synthesized in good to excellent yield. H/D exchange reaction was exemplified by the model reaction of acetophenone in deuterium containing methanol. Factors influencing the effectiveness of the hydrogen/deuterium exchange reaction of the methyl group were determined. The cascade procedure bears the potential to overcome the limitations of conventional synthesis and unlocks practical use in the synthesis of deuterium-labeled pharmaceuticals.

deuteration reaction, heteroatom-substituted secondary phosphine oxide (HASPO) ligands, hydrogen/deuterium exchange, platinum complexes, hydration reaction of alkynes

http://dx.doi.org/10.1002/aoc.7336

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