A molecular electron density theory study of the chemo- and regioselective [3+2] cycloaddition reactions between trifluoroacetonitrile N-oxide and thioketones

被引：11
作者：
Emamian, Saeedreza [1 ]
Lu, Tian [2 ]
Domingo, Luis. R. [3 ]
Saremi, Leily Heidarpoor [4 ]
Rios-Gutierrez, Mar [3 ]
机构：
[1] Islamic Azad Univ, Shahrood Branch, Dept Chem, Shahrood, Iran
[2] Beijing Kein Res Ctr Nat Sci, Beijing 100022, Peoples R China
[3] Univ Valencia, Dept Organ Chem, Dr Moliner 50, E-46100 Valencia, Spain
[4] Univ Sistan & Baluchestan, Dept Chem, Fac Sci, Zahedan, Iran
来源：
CHEMICAL PHYSICS | 2018年 / 501卷
关键词：
3+2] cycloaddition reactions; Nitrile N-oxides; Chemoselectivity; Regioselectivity; ELF topological analysis; Molecular Electron Density Theory (MEDT); ZETA VALENCE QUALITY; NONCOVALENT INTERACTIONS; THERMOCHEMICAL KINETICS; BASIS-SETS; AB-INITIO; MECHANISM; REACTIVITY; RING; DFT;
D O I：
10.1016/j.chemphys.2017.12.019
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
The [3 + 2] cycloaddition (32CA) reaction between trifluoroacetonitrile N-oxide (NO 7) and 2,2,4,4-tetramethyl-3-thioxocyclobutan-1-one (THK 12) as well as the self-dimerization of NO 7 as a competitive pathway were studied within the Molecular Electron Density Theory (MEDT) using several DFT functionals together with def2-TZVP basis set. Taking CCSD(T)/TZVP activation energies as reference, among the employed functionals, just the B2PLYP-D3(BJ) one is able to portray complete predominance of 32CA reaction over self-dimerization process in excellent agreement with the experimental outcomes. Analysis of the global reactivity indices permits to characterize NO 7 and THK 12 as a strong electrophile and a strong nucleophile, respectively, while analysis of the Parr functions allows explaining the chemo- and regioselectivity observed experimentally. The electron localization function (ELF) analysis of several points along the IRC profile associated with the energetically most favorable reaction channel permits to establish a non-concerted two-stage one-step molecular mechanism for this polar pmr-type 32CA reaction. (C) 2018 Elsevier B.V. All rights reserved.
引用
收藏
页码：128 / 137
页数：10
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