Quantum mechanical investigation of the Mechanism of Nickel-Catalyzed Cycloaddition Reaction of 3-azetidinone with Alkynes

Authors

  • ahmad sotal tishreen university
  • Mohammad Abd Al-Hakim badawi Tishreen University

Abstract

The reaction mechanism of the 3-azetidinone with nickel-catalyzed alkenes was studied using the function M06-2X with two basis sets: def2-TSVP and LANL2DZ for the nickel atom with two basis sets def2-SVP and 6-31G(d) for the main elements atoms. The computational results indicate that the reaction takes place through two independent pathways, one of which is linked by the coordination of 1-Boc-3-azetidinone on the Ni(0) center to form an intermediate state that includes the Ni–C(O) bond, then the insertion of the alkyne to the Ni–CO bond (pathway 1), As for pathway 2, it is related to the coordination of the 1-Boc-3-azetidinone on the Ni(0) center to form an intermediate state that includes the Ni–C(sp3) bond, and then the insertion of the alkyne to the Ni–C(sp3) bond.
Analysis of the global nucleophilic and electrophilic indices of the reagents indicates that the nickel complex shows a strong nucleophilic role, while the compound 3-azetidinone shows an electrophilic role, and that the reaction is polar in its nature. In addition, the local electrophilic and nucleophile indices of the reactants indicate that the nickel atom in the complex is the most nucleophilic center, while the carbon atom C(=O) in the compound 3-azetidinone is the most electrophilic center, and thus, pathway 1 More likely than Pathawy 2. The computational results of our studies are consistent with previous research with the exception that the mechanism proceeds through two independent pathways; That is, there are no common transitional or intermediate states in the two pathways, and this contradicts what was indicated in previous computer studies

 

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Published

2024-04-23

How to Cite

1.
سوتل أ, بدوي معا. Quantum mechanical investigation of the Mechanism of Nickel-Catalyzed Cycloaddition Reaction of 3-azetidinone with Alkynes. TUJ-BA [Internet]. 2024Apr.23 [cited 2024May6];46(1):77-91. Available from: https://journal.tishreen.edu.sy/index.php/bassnc/article/view/15263

Issue

Vol. 46 No. 1 (2024): Tishreen University Journal of Research and Scientific Studies - Basic Sciences Series

Section

Master student researches

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