自然轨道福井函数和成键活性描述符应用于解释苯硫醌和1, 3-二烯的[2+4]和[4+2]环加成反应中的成键机理

doi:10.3866/PKU.WHXB201709222

Abstract

Abstract:

o-Thioquinones can undergo either [2+4] or [4+2] cycloaddition reactions with acyclic dienes. To illustrate the bonding processes in these cycloadditions, the natural orbital Fukui function (NOFF) and bonding reactivity descriptor have been employed. The electrophilicity of a bond or an orbital in the o-thioquinone as well as in the acyclic diene has been found using the NOFF, which suggests that electron transfer takes place from an electron-donating bonding orbital to an electron-accepting antibonding/bonding orbital, leading to the cyclic product via the formation of a circular loop and two covalent bonds. The bonding reactivity descriptor shows that covalent bonds readily form between atom k1 of one molecule with a large f_k1⁺ value and atom k2 of another molecule with a large f_k2^- value. Both the NOFF and the bonding reactivity descriptor are efficient tools for interpreting the mechanism underlying the [2+4] and [4+2] cycloaddition between o-thioquinones and acyclic dienes.

Key words: Fukui function, Natural orbital Fukui function (NOFF), Bonding reactivity descriptor, Cycloaddition, Nucleophilic/electrophilic attack

Chaoxian YAN,Fan YANG,Ruizhi WU,Dagang ZHOU,Xing YANG,Panpan ZHOU. Application of Natural Orbital Fukui Functions and Bonding Reactivity Descriptor in Understanding Bond Formation Mechanisms Underlying [2+4] and [4+2] Cycloadditions of o-Thioquinones with 1, 3-Dienes[J]. Acta Phys. -Chim. Sin. 2018, 34(5), 497-502. doi: 10.3866/PKU.WHXB201709222

References

1	Chapman O. L. ; McIntosh C. L. J. Chem. Soc. D 1971, 383.
2	Mayo P. D. ; Weedon A. C. ; Wong G. S. K. J.Org. Chem. 1979, 44, 1977.
3	Schulz R. ; Schweig A. Angew. Chem. Int. Ed. 1981, 20, 570.
4	Naghipur A. ; Reszka K. ; Sapse A.-M. ; Lown J. W. J.Am. Chem. Soc. 1989, 111, 258.
5	Capozzi G. ; Dios A. ; Franck R. W. ; Geer A. ; Marzabaldi C. ; Menichetti S. ; Nativi C. ; Tamarez M. Angew. Chem. Int. Ed. 1996, 35, 777.
6	Capozzi G. ; Falciani C. ; Menichetti S. ; Nativi C. J.Org. Chem. 1997, 62, 2611.
7	Capozzi G. ; Falciani C. ; Menichetti S. ; Nativi C. ; Raffaelli B. Chem. Eur. J. 1999, 5, 1748.
8	Capozzi G. ; Lo Nostro P. ; Menichetti S. ; Nativi C. ; Sarri P. Chem. Commun. 2001, 551.
9	Nair V. ; Mathew B. ; Radharkrishnan K. V. ; Rath N. P. Synlett 2000, 61.
10	Nair V. ; Mathew B. Tetrahedron Lett. 2000, 41, 6919.
11	Nair V. ; Mathew B. ; Rath N. P. ; Vairamani M. ; Prabhakar S. Tetrahedron 2001, 57, 8349.
12	Nair V. ; Mathew B. ; Menon R. S. ; Mathew S. ; Vairamani M. ; Prabhakar S. Tetrahedron 2002, 58, 3235.
13	Nair V. ; Mathew B. ; Thomas S. ; Vairamani M. ; Prabhakar S. J. Chem. Soc., Perkin Trans. 1 2001, 3020.
14	Menichetti S. ; Viglianisi C. Tetrahedron 2003, 59, 5523.
15	Contini A. ; Leone S. ; Menichetti S. ; Viglianisi C. ; Trimarco P. J.Org. Chem. 2006, 71, 5507.
16	Reed A. E. ; Curtiss L. A. ; Weinhold F. Chem. Rev. 1988, 88, 899.
17	Zhou P. ; Ayers P. W. ; Liu S. ; Li T. Phys. Chem. Chem. Phys. 2012, 14, 9890.
18	Priya A. M. ; Senthilkumar L. RSC Adv. 2014, 4, 23464.
19	Yang W. ; Mortier W. J. J.Am. Chem. Soc. 1986, 108, 5708.
20	Liu S. Acta Phys. -Chim. Sin. 2009, 25, 590.
20	刘述斌. 物理化学学报, 2009, 25, 590.
21	Parr R. G. ; Yang W. J.Am. Chem. Soc. 1984, 106, 4049.
22	Yang W. ; Parr R. G. ; Pucci R. J.Chem. Phys. 1984, 81, 2862.
23	Albright T. A. ; Burdett J. K. ; Whangbo M. H. Orbital Interactions in Chemistry Wiley-Interscience: New York, NY, USA 1985.
24	Fujimoto H. ; Fukui K. ; Klopman G. Chemical Reactivity and Reaction Paths Wiley-Interscience: New York, NY, USA 1974.
25	Parr R. G. ; Yang W. Density-Functional Theory of Atoms and Molecules Oxford University Press: New York, NY, USA 1989.
26	Anderson J. S. M. ; Melin J. ; Ayers P. W. J.Chem. Theory Comput. 2007, 3, 358.
27	Ayers P. W. Faraday Discuss. 2007, 135, 161.
28	Berkowitz M. J.Am. Chem. Soc. 1987, 109, 4823.
29	Zhou P.-P. ; Liu S. ; Ayers P. W. ; Zhang R. -Q. J. Chem. Phys. 2017.
30	Frisch M. J. ; Trucks G. W. ; Schlegel H. B. ; Scuseria G. E. ; Robb M. A. ; Cheeseman J. R. ; Scalmani G. ; Barone V. ; Mennucci B. ; Petersson G. A. ; et al Gaussian 09, Revision D., 01, Gaussian, Inc.: Wallingford CT, 2013.
31	Becke A. D. J.Chem. Phys. 1993, 98, 5648.
32	Lee C. ; Yang W. ; Parr R. G. Phys. Rev. B 1988, 37, 785.
33	Foster J. P. ; Weinhold F. J.Am. Chem. Soc. 1980, 102, 7211.
34	Reed A. E. ; Weinstock R. B. ; Weinhold F. J.Chem. Phys. 1985, 83, 735.
35	Roy R. K. ; Hirao K. ; Krishnamurty S. ; Pal S. J.Chem. Phys. 2001, 115, 2901.
36	Roy R. K. ; Hirao K. ; Pal S. J.Chem. Phys. 2000, 113, 1372.
37	Roy R. K. ; Pal S. ; Hirao K. J.Chem. Phys. 1999, 110, 8236.
38	Bultnick P. ; Carbó-Dorca R. J.Math. Chem. 2003, 34, 67.
39	Bultnick P. ; Carbó-Dorca R. ; Langenaeker W. J.Chem. Phys. 2003, 118, 4349.
40	Ayers P. W. ; Morell C. ; De Proft F. ; Geerlings P. Chem. Eur. J. 2007, 13, 8240.
41	Geerlings P. ; Proft F. D. ; Langenaeker W. Chem. Rev. 2003, 103, 1793.
42	Chattaraj P. K. ; Sarkar U. ; Roy D. R. Chem. Rev. 2006, 106, 2065.
43	Chermette H. J.Comput. Chem. 1999, 20, 129.
44	Parr R. G. ; Yang W. Annu. Rev. Phys. Chem. 1995, 46, 701.

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Application of Natural Orbital Fukui Functions and Bonding Reactivity Descriptor in Understanding Bond Formation Mechanisms Underlying [2+4] and [4+2] Cycloadditions of o-Thioquinones with 1, 3-Dienes

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