Nasir RASOOL, Kulsoom Ghulam ALI, Hafiz Mansoor IKRAM, Tariq MAHMOOD, Gulraiz AHMAD, Muhammad Arfan ANJUM, Muhammad ZUBAIR, Muhammad Ali HASHMI

Density functional theory-supported studies of structural and electronic properties of substituted-phenol derivatives synthesized by efficient O- or C-arylation via Chan–Lam or Suzuki cross-coupling reactions

The present study reports the efficient synthesis and computational studies of the structural and electronicproperties of some interesting substituted phenol derivatives. Efficient and versatile procedures to synthesize a seriesof diaryl ether derivatives (2a–2c, 4a–4h) and bis-arylated products (5a–5c) are described. In this manuscript, usingthe commercially available starting material 1 and 3, a 1-step approach was developed by means of Cu(II)-mediatedChan–Lam and Pd-catalyzed Suzuki cross-coupling reactions to synthesize diaryl ether and bis-arylated products withmoderate to good yields. The starting substrates, 2-bromo-4-methylphenol 1 or 2,4-dibromophenol 3, were both treatedwith several arylboronic acids, which led to the development of new carbon-oxygen bonds through Chan–Lam reactions.In addition, the hydroxyl group of 2,4-dibromophenol 3 was protected with isopropyl bromide to produce 4, which wasthen treated with arylboronic acids to synthesize the corresponding bis-arylated products through Suzuki cross-couplingreactions. Density functional theory calculations provided insight into the structural and electronic properties of thesynthesized compounds. An analysis of the frontier orbitals and other reactivity descriptors, including the ionizationpotential, electron affinity, chemical hardness, electronic chemical potential, and electrophilicity index, is presented,which shows that compound 4c was the most reactive, while 4f and 4h were the most stable.

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