Theoretical Study on the Origin of Abnormal Regioselectivity in Ring-Opening Reaction of Hexafluoropropylene Oxide (2024)

1. the Ministry of Science and Technology of China
2. the Natural Science Foundation of China

1. Gomes, Epoxide containing molecules: A good or a bad drug design approach, Eur. J. Med. Chem., № 201, с. 112327
   https://doi.org/10.1016/j.ejmech.2020.112327
2. Sugimoto, Copolymerization of carbon dioxide and epoxide, J. Polym. Sci. Part A: Polym. Chem., № 42, с. 5561
   https://doi.org/10.1002/pola.20319
3. Brocas, Polyether synthesis: From activated or metal-free anionic ring-opening polymerization of epoxides to functionalization, Prog. Polym. Sci., № 38, с. 845
   https://doi.org/10.1016/j.progpolymsci.2012.09.007
4. Schneider, Synthesis of 1,2-Difunctionalized Fine Chemicals through Catalytic, Enantioselective Ring-Opening Reactions of Epoxides, Synthesis, № 23, с. 3919
   https://doi.org/10.1055/s-2006-950348
5. Vilotijevic, Epoxide-opening cascades in the synthesis of polycyclic polyether natural products, Angew. Chem. Int. Ed., № 48, с. 5250
   https://doi.org/10.1002/anie.200900600
6. Vilotijevic, Synthesis of marine polycyclic polyethers via endo-selective epoxide-opening cascades, Mar. Drugs, № 8, с. 763
   https://doi.org/10.3390/md8030763
7. Jat, Isomerization of Epoxides, Adv. Synth. Catal., № 361, с. 4426
   https://doi.org/10.1002/adsc.201900392
8. Talukdar, Synthetically important ring opening reactions by alkoxybenzenes and alkoxynaphthalenes, RSC. Adv., № 10, с. 31363
   https://doi.org/10.1039/D0RA05111J
9. Morgan, Thermochemical studies of epoxides and related compounds, J. Org. Chem., № 78, с. 4303
   https://doi.org/10.1021/jo4002867
10. Parker, Mechanisms of Epoxide Reactions, Chem. Rev., № 59, с. 737
    https://doi.org/10.1021/cr50028a006
11. Carey, F.A., and Sundberg, R.J. (2007). Advanced Organic Chemistry Part A: Structureand Mechanisms, Springer. [5th ed.].
12. Millauer, Hexafluoropropene Oxide—A Key Compound in Organofluorine Chemistry, Angew. Chem. Int. Ed., № 24, с. 161
    https://doi.org/10.1002/anie.198501611
13. Eleuterio, Polymerization of Perfluoro Epoxides, J. Macromol. Sci. Part A Pure Appl. Chem., № 6, с. 1027
    https://doi.org/10.1080/10601327208056884
14. Sianesi, The Chemistry of Hexafluoropropene Epoxide, J. Org. Chem., № 31, с. 2312
    https://doi.org/10.1021/jo01345a054
15. Ishikawa, Preparation of Perfluoroalkylated Benzoheterocyclic Compounds Using Hexafluoro-1,2-epoxypropane, Bull. Chem. Soc. Jpn., № 50, с. 2164
    https://doi.org/10.1246/bcsj.50.2164
16. Coe, Reactions involving hexafluoropropylene oxide: Novel ring opening reactions and resolution of a racemic mixture of a bromofluoro ester, ultrasound mediated Reformatsky reactions and stereoselectivity, J. Chem. Soc. Perkin Trans., № 17, с. 2803
    https://doi.org/10.1039/a804097d
17. Hill, Polymers from Hexafluoropropylene Oxide (HFPO), J. Macromol. Sci. Part A: Pure Appl. Chem., № 8, с. 499
    https://doi.org/10.1080/00222337408065846
18. Koyama, Synthesis of Crystalline CF3-Rich Perfluoropolyethers from Hexafluoropropylene Oxide and (Trifluoromethyl)Trimethylsilane, Macromol. Rapid. Commun., № 43, с. 2200038
    https://doi.org/10.1002/marc.202200038
19. Zapevalov, A., Filyakova, T., and Kolenko, I. (1988, January 25–26). Abstracts of papers. Proceedings of the Fifth Regular Meeting of Soviet-Japanese Fluorine Chemists, Tokyo, Japan.
20. Huang, W. (1996). Organofluorine Chemistry in China, Shanghai Scientific and Technical Publisher.
21. Furuyama, Kinetic Study of the Reaction CHI3 + HI ⇄ CH2I2 + I2. A Summary of Thermochemical Properties of Halomethanes and Halomethyl Radicals, J. Am. Chem. Soc., № 91, с. 7564
    https://doi.org/10.1021/ja50001a003
22. Egger, hom*opolar and Heteropolar Bond Dissociation Energies and Heats of Formation of Radicals and Ions in the Gas Phase II. The relationship between structure and bond dissociation in organic molecules, Helv. Chim. Acta, № 56, с. 1537
    https://doi.org/10.1002/hlca.19730560510
23. Petrov, V.A. (2009). Fluorinated Heterocyclic Compounds, John Wiley & Sons, Inc.
    https://doi.org/10.1002/9780470528952
24. Rauhut, Chemical Reactivity Controlled by Negative Hyperconjugation: A Theoretical Study, Chem. Eur. J., № 9, с. 3143
    https://doi.org/10.1002/chem.200304878
25. Wang, Fluorine Effects on Group Migration via a Rhodium(V) Nitrenoid Intermediate, Angew. Chem. Int. Ed., № 56, с. 14918
    https://doi.org/10.1002/anie.201708505
26. Suenaga, A natural bond orbital analysis of aryl-substituted polyfluorinated carbanions: Negative hyperconjugation, J. Phys. Org. Chem., № 31, с. e3721
    https://doi.org/10.1002/poc.3721
27. Alabugin, Stereoelectronic power of oxygen in control of chemical reactivity: The anomeric effect is not alone, Chem. Soc. Rev., № 50, с. 10253
    https://doi.org/10.1039/D1CS00386K
28. Farnham, Crystal and molecular structure of tris(dimethylamino)sulfonium trifluoromethoxide. Evidence for negative fluorine hyperconjugation, J. Am. Chem. Soc., № 107, с. 4565
    https://doi.org/10.1021/ja00301a043
29. Dixon, Structures and stabilities of fluorinated carbanions. Evidence for anionic hyperconjugation, J. Am. Chem. Soc., № 108, с. 4027
    https://doi.org/10.1021/ja00274a029
30. Levandowski, Hyperconjugative pi --> sigma*(CF) Interactions Stabilize the Enol Form of Perfluorinated Cyclic Keto-Enol Systems, J. Org. Chem., № 84, с. 6432
    https://doi.org/10.1021/acs.joc.9b00825
31. Zhou, Mechanism of Silver-Mediated Geminal Difluorination of Styrenes with a Fluoroiodane Reagent: Insights into Lewis-Acid-Activation Model, Org. Lett., № 18, с. 6128
    https://doi.org/10.1021/acs.orglett.6b03134
32. Yan, Mechanism and Origin of the Unexpected Chemoselectivity in Fluorocyclization of o-Styryl Benzamides with a Hypervalent Fluoroiodane Reagent, J. Org. Chem., № 81, с. 9006
    https://doi.org/10.1021/acs.joc.6b01642
33. Li, Quantitative Scale for the Trifluoromethylthio Cation-Donating Ability of Electrophilic Trifluoromethylthiolating Reagents, Org. Lett., № 18, с. 264
    https://doi.org/10.1021/acs.orglett.5b03433
34. Li, An Energetic Guide for Estimating Trifluoromethyl Cation Donor Abilities of Electrophilic Trifluoromethylating Reagents: Computations of X-CF3 Bond Heterolytic Dissociation Enthalpies, J. Org. Chem., № 81, с. 3119
    https://doi.org/10.1021/acs.joc.5b02821
35. Li, A Systematic Assessment of Trifluoromethyl Radical Donor Abilities of Electrophilic Trifluoromethylating Reagents, Asian J. Org. Chem., № 6, с. 235
    https://doi.org/10.1002/ajoc.201600539
36. Li, Mechanism and Origins of Stereoinduction in Natural Cinchona Alkaloid Catalyzed Asymmetric Electrophilic Trifluoromethylthiolation of β-Keto Esters with N-Trifluoromethylthiophthalimide as Electrophilic SCF3 Source, ACS Catal., № 7, с. 7977
    https://doi.org/10.1021/acscatal.7b03007
37. Li, Establishing the Trifluoromethylthio Radical Donating Abilities of Electrophilic SCF(3)-Transfer Reagents, J. Org. Chem., № 82, с. 8697
    https://doi.org/10.1021/acs.joc.7b01771
38. Yang, A Systematic Evaluation of the N-F Bond Strength of Electrophilic N-F Reagents: Hints for Atomic Fluorine Donating Ability, J. Org. Chem., № 82, с. 4129
    https://doi.org/10.1021/acs.joc.7b00036
39. Zhou, Theoretical study of Lewis acid activation models for hypervalent fluoroiodane reagent: The generality of "F-coordination” activation model, Tetrahedron Lett., № 58, с. 1287
    https://doi.org/10.1016/j.tetlet.2017.02.040
40. Li, Computational Study of the Trifluoromethyl Radical Donor Abilities of CF3 Sources, Acta Chim. Sin., № 76, с. 988
    https://doi.org/10.6023/A18080334
41. Zhou, Mechanism and Origins of Chemo- and Stereoselectivities of Aryl Iodide-Catalyzed Asymmetric Difluorinations of beta-Substituted Styrenes, J. Am. Chem. Soc., № 140, с. 15206
    https://doi.org/10.1021/jacs.8b05935
42. Li, Origin of Stereocontrol in Photoredox Organocatalysis of Asymmetric alpha-Functionalizations of Aldehydes, J. Org. Chem., № 83, с. 3333
    https://doi.org/10.1021/acs.joc.8b00469
43. Zhang, Exploration of the Synthetic Potential of Electrophilic Trifluoromethylthiolating and Difluoromethylthiolating Reagents, Angew. Chem. Int. Ed., № 57, с. 12690
    https://doi.org/10.1002/anie.201805859
44. Li, Ordering the relative power of electrophilic fluorinating, trifluoromethylating, and trifluoromethylthiolating reagents: A summary of recent efforts, Tetrahedron Lett., № 59, с. 1278
    https://doi.org/10.1016/j.tetlet.2018.02.039
45. Kang, Quantification of the Activation Capabilities of Lewis/Brønsted Acid for Electrophilic Trifluoromethylthiolating Reagents, Chin. J. Chem., № 38, с. 130
    https://doi.org/10.1002/cjoc.201900412
46. Li, Establishing Cation and Radical Donor Ability Scales of Electrophilic F, CF(3), and SCF(3) Transfer Reagents, Acc. Chem. Res., № 53, с. 182
    https://doi.org/10.1021/acs.accounts.9b00393
47. Zheng, The Acidities of Nucleophilic Monofluoromethylation Reagents: An Anomalous α-Fluorine Effect, Angew. Chem. Int. Ed., № 60, с. 9401
    https://doi.org/10.1002/anie.202015614
48. Zheng, Computational insights into the effects of reagent structure and bases on nucleophilic monofluoromethylation of aldehydes, Chin. Chem. Lett., № 33, с. 2387
    https://doi.org/10.1016/j.cclet.2021.11.045
49. Bickelhaupt, Understanding reactivity with Kohn-Sham molecular orbital theory: E2-SN2 mechanistic spectrum and other concepts, J. Comput. Chem., № 20, с. 114
    https://doi.org/10.1002/(SICI)1096-987X(19990115)20:1<114::AID-JCC12>3.0.CO;2-L
50. Bickelhaupt, Analyzing Reaction Rates with the Distortion/Interaction-Activation Strain Model, Angew. Chem. Int. Ed., № 56, с. 10070
    https://doi.org/10.1002/anie.201701486
51. Vermeeren, Understanding chemical reactivity using the activation strain model, Nat. Protoc., № 15, с. 649
    https://doi.org/10.1038/s41596-019-0265-0
52. Glendening, Natural bond orbital methods, Wires. Comput. Mol. Sci., № 2, с. 1
    https://doi.org/10.1002/wcms.51
53. Glendenning, E., Reed, A., Carpenter, J., and Weinhold, F. (2022, October 02). NBO Version 3.1, Madison, WI, USA. Available online: https://www.cup.uni-muenchen.de/ch/compchem/pop/nbo2.html.
54. Beagley, Gas-phase electron diffraction determination of the molecular structure of perfluoro(methyloxirane), J. Fluorine Chem., № 18, с. 159
    https://doi.org/10.1016/S0022-1139(00)82312-X
55. Parr, Electrophilicity Index, J. Am. Chem. Soc., № 121, с. 1922
    https://doi.org/10.1021/ja983494x
56. Conceptual Density Functional Theory and Some Recent Developments, Acta. Phys. Chim. Sin., № 25, с. 590
    https://doi.org/10.3866/PKU.WHXB20090332
57. Hansen, Regioselectivity of Epoxide Ring-Openings via SN2 Reactions Under Basic and Acidic Conditions, Eur. J. Org. Chem., № 25, с. 3822
    https://doi.org/10.1002/ejoc.202000590
58. Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Petersson, G.A., and Nakatsuji, H. (2022, October 02). Gaussian 16 Rev. A.03, Wallingford, CT, USA. Available online: https://gaussian.com/citation_a03/.
59. Clark, Efficient diffuse function-augmented basis sets for anion calculations. III. The 3-21+G basis set for first-row elements, Li-F, J. Comput. Chem., № 4, с. 294
    https://doi.org/10.1002/jcc.540040303
60. Frisch, Self-consistent molecular orbital methods 25. Supplementary functions for Gaussian basis sets, J. Chem. Phys., № 80, с. 3265
    https://doi.org/10.1063/1.447079
61. Hariharan, Accuracy of AHn equilibrium geometries by single determinant molecular orbital theory, Mol. Phys., № 27, с. 209
    https://doi.org/10.1080/00268977400100171
62. Chai, Long-range corrected hybrid density functionals with damped atom-atom dispersion corrections, Phys. Chem. Chem. Phys., № 10, с. 6615
    https://doi.org/10.1039/b810189b
63. Marenich, Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions, J. Phys. Chem. B., № 113, с. 6378
    https://doi.org/10.1021/jp810292n
64. Galabov, Nucleophilic Influences and Origin of the S(N)2 Allylic Effect, Chem. Eur. J., № 24, с. 11637
    https://doi.org/10.1002/chem.201801187
65. Grimme, A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu, J. Chem. Phys., № 132, с. 154104
    https://doi.org/10.1063/1.3382344
66. Gonzales, Assessment of Density Functional Theory for Model SN2 Reactions: CH3X + F− (X = F, Cl, CN, OH, SH, NH2, PH2), J. Phys. Chem. A, № 105, с. 11327
    https://doi.org/10.1021/jp012892a
67. McLean, Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z = 11–18, J. Chem. Phys., № 72, с. 5639
    https://doi.org/10.1063/1.438980
68. Johnson, NCIPLOT: A program for plotting non-covalent interaction regions, J. Chem. Theory Comput., № 7, с. 625
    https://doi.org/10.1021/ct100641a
69. Lu, Multiwfn: A multifunctional wavefunction analyzer, J. Comput. Chem., № 33, с. 580
    https://doi.org/10.1002/jcc.22885
70. Liu, S. (2022). Conceptual Density Functional Theory, WILEY-VCH GmbH.
    https://doi.org/10.1002/9783527829941
71. Svatunek, autoDIAS: A python tool for an automated distortion/interaction activation strain analysis, J. Comput. Chem., № 40, с. 2509
    https://doi.org/10.1002/jcc.26023
72. Schrödinger, LLC (2022, October 01). The PyMOL Molecular Graphics System, Version 2.0.4. Available online: http://www.pymol.org/pymol.
73. Legault, C.Y. (2022, October 10). Université de Sherbrooke, CYLview20. Available online: https://www.cylview.org.
74. Ni, The unique fluorine effects in organic reactions: Recent facts and insights into fluoroalkylations, Chem. Soc. Rev., № 45, с. 5441
    https://doi.org/10.1039/C6CS00351F
75. Liu, A novel type of donor–acceptor cyclopropane with fluorine as the donor: (3 + 2)-cycloadditions with carbonyls, Chem. Sci., № 13, с. 2686
    https://doi.org/10.1039/D2SC00302C
76. Wu, Mechanisms of Rhodium (III)-Catalyzed C–H Functionalizations of Benzamides with α,α-Difluoromethylene Alkynes, J. Org. Chem., № 83, с. 9220
    https://doi.org/10.1021/acs.joc.8b01229
77. Kang, Fluorine Effects for Tunable C–C and C–S Bond Cleavage in Fluoro-Julia–Kocienski Intermediates, CCS Chem., № 3, с. 1678
    https://doi.org/10.31635/ccschem.020.202000320
78. Peng, Esterification of Carboxylic Acids with Difluoromethyl Diazomethane and Interrupted Esterification with Trifluoromethyl Diazomethane: A Fluorine Effect, Org. Lett., № 19, с. 5689
    https://doi.org/10.1021/acs.orglett.7b02866
79. Geerlings, Conceptual density functional theory, Chem. Rev., № 103, с. 1793
    https://doi.org/10.1021/cr990029p
80. Rong, Comparing Methods for Predicting the Reactive Site of Electrophilic Substitution, Acta Phys. Chim. Sin., № 30, с. 628
    https://doi.org/10.3866/PKU.WHXB201401211
81. Domingo, Applications of the Conceptual Density Functional Theory Indices to Organic Chemistry Reactivity, Molecules, № 21, с. 748
    https://doi.org/10.3390/molecules21060748
82. Parr, Density functional approach to the frontier-electron theory of chemical reactivity, J. Am. Chem. Soc., № 106, с. 4049
    https://doi.org/10.1021/ja00326a036
83. Yang, The use of global and local molecular parameters for the analysis of the gas-phase basicity of amines, J. Am. Chem. Soc., № 108, с. 5708
    https://doi.org/10.1021/ja00279a008
84. Morell, New dual descriptor for chemical reactivity, J. Phys. Chem. A, № 109, с. 205
    https://doi.org/10.1021/jp046577a

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