First Exclusive Stereo- and Regioselective Preparation of 5-Arylimino-1,3,4-Selenadiazole Derivatives: Synthesis, NMR analysis, and Computational Studies

Ziad Moussa; Alejandro Perez Paz; Mohamed A Khalaf; Zaher M A Judeh; Ahmed Alzamly; Abdelouahid Samadi; Jabir H Al-Fahemi; Madhu Babu Tatina; Harbi Tomah Al-Masri; Rabab S Jassas; Saleh A Ahmed

doi:10.1002/asia.202300475

First Exclusive Stereo- and Regioselective Preparation of 5-Arylimino-1,3,4-Selenadiazole Derivatives: Synthesis, NMR analysis, and Computational Studies

Chem Asian J. 2023 Sep 1;18(17):e202300475. doi: 10.1002/asia.202300475. Epub 2023 Aug 8.

Authors

Affiliations

¹ Department of Chemistry, College of Science, United Arab Emirates University, P. O. Box 15551, Al Ain, United Arab Emirates.
² School of Chemical and Biomedical Engineering, Nanyang Technological University, 62 Nanyang Drive, N1.2-B1-14, Singapore, 637459, Singapore.
³ Department of Chemistry, Faculty of Applied Sciences, Umm Al-Qura University, Makkah, 21955, Saudi Arabia.
⁴ Division of Organic Synthesis & Process Chemistry, CSIR-Indian Institute of Chemical Technology (CSIR-IICT), Hyderabad, Telangana, 500007, India.
⁵ Department of Chemistry, Faculty of Sciences, Al al-Bayt University, P. O. Box 130040, Mafraq, 25113, Jordan.
⁶ Department of Chemistry, Jamoum University College, Umm Al-Qura University, 21955, Makkah, Saudi Arabia.
⁷ Department of Chemistry, Faculty of Science, Assiut University, 71516, Assiut, Egypt.

PMID: 37495559
DOI: 10.1002/asia.202300475

Abstract

Isoselenocyanates are valuable coupling partners required for preparing key chemical intermediates and biologically active molecules in an accelerated and effective way. Likewise, (Z)-2-oxo-N-phenylpropanehydrazonoyl chlorides have been employed in numerous one-step heteroannulation reactions to assemble the structural core of several various kinds of heterocyclic compounds. Here, we describe the inverse electron demand 1,3-dipolar cycloaddition reaction of isoselenocyanates with a variety of substituted (Z)-2-oxo-N-phenylpropanehydrazonoyl chlorides to generate, regioselectively and stereoselectively, a series of 5-arylimino-1,3,4-selenadiazole derivatives comprising a multitude of functional groups on both aryl rings. The synthetic method features gentle room-temperature conditions, wide substrate scope, and good to high reaction yields. The selenadiazoles were separated by gravity filtration in all instances and chemical structures were validated by multinuclear NMR spectroscopy and high accuracy mass spectral measurements. First conclusive molecular structure elucidation of the observed 5-arylimino-selenadiazole regioisomer was verified by single-crystal X-ray diffraction analysis. Crystal-structure measurement was successfully carried out on (Z)-1-(4-(4-iodophenyl)-5-(p-tolylimino)-4,5-dihydro-1,3,4-selenadiazol-2-yl)ethan-1-one and (Z)-1-(5-((4-methoxyphenyl)imino)-4-(4-(methylthio)phenyl)-4,5-dihydro-1,3,4-selenadiazol-2-yl)ethan-1-one. Likewise, the (Z)-geometry of the hydrazonoyl chloride reactant was proven by X-ray diffraction studies. As representative examples, crystal-structure determination was carried out on (Z)-2-oxo-N-phenylpropanehydrazonoyl chloride and (Z)-N-(3,5-bis(trifluoromethyl)phenyl)-2-oxopropanehydrazonoyl chloride. Density functional theory calculations at the B3LYP-D4/def2-TZVP level were conducted to support the noted experimental findings and suggested mechanism.

Keywords: density functional theory; hydrazonoyl chloride; inverse electron demand 1,3-dipolar cycloadditions, 1,3,4-selenadiazole; isoselenocyanate.

Grants and funding

22UQU4320545DSR08/Deanship of Scientific Research at Umm Al-Qura University