Stereoselective epoxidation of cis-3,4-disubstituted-(CH2X)- cyclobutenes with dimethyldioxirane and peroxy acids. Experimental and computational evidence for a syn-orienting electrostatic effect

Tetrahedron

Volumn 55, Issue 37, 1999, Pages 11309-11330

  Freccero, Mauro ^a   Gandolfi, Remo ^a   Sarzi Amadè, Mirko ^a  

^a UNIVERSITY OF PAVIA   (Italy)

Author keywords

Cycloalkenes; Dioxiranes; Epoxidation; Transition states

Indexed keywords

ALKENE; CYCLOBUTANE DERIVATIVE; ETHYLENE OXIDE DERIVATIVE; FORMIC ACID DERIVATIVE; OXYGEN; PEROXIDE;

ARTICLE; CALCULATION; ELECTRICITY; ELECTRON; EPOXIDATION; EXPERIMENT; PRIORITY JOURNAL; REACTION ANALYSIS; STEREOCHEMISTRY;

THIA;

EID: 0033543498     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4020(99)00630-4     Document Type: Article

References (39)

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28. Tricycle epoxysulfites such as 15a, 15s, and 16a are a novelty in the current literature. To our knowledge no other epoxysulfites have been published before. For the above reasons details of data collections, structure refinements and theoretical calculation (B3LYP/6-31G*) related to the above structures have been submitted as full paper to Zeitschrift für Kristallographie.
29. Gaussian 94, Revision E.3, M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. B. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez, and J. A. Pople, Gaussian, Inc., Pittsburgh PA, 1995.
30. Cyclic sulfites 7, 8 and 5H show a syn pyramidalization of the olefinic carbon (anti bending of the olefinic hydrogens) higher than 1. For conformers (o)-7, (i)-7, (o)-8 and (i)-8 the α angles (B3LYP/6-31G*) are -2.1, -1.2, -2.2 and -1.4° respectively. The two most stable conformation of 5H (5H' and 5H") show an even higher pyramidalization with α angles of -2.3° and -3.0°. The α values in the calculated TSs (B3LYP/6-31G*) are as follows: DHD-1a +6.4°, DHD-1s -7.9°, DHD-1a +7.2°, DHD-1s -8.2°, DHD-7a +6.7°, DHD-7s -9.0°, DHD-8a +7.7°, DHD-8s -11.1°, DHD-5H'a +14.5°, +1.0°, DHD-5H's -8.4°, -8.1° (two different α values are reported because the TSs DHD-5H'a and DHD-5H's are asynchronous). DHD-5H"a +8.0°, DHD-5H"s -9.1°, anti,exo-1 +6.7°, syn,exo-1 -8.4°, anti,endo-1 +7.8°, syn,endo-1 -10.45°.
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35. Activation thermodynamic parameters are as follows: DHD-1a, ΔH≠ = 44.89 kJ/mol, ΔS≠ = -116.06 J/mol K, ΔG≠ = 79.45 kJ/mol; DHD-1s, ΔH≠ = 41.00 kJ/mol, ΔS≠ = -119.75 J/mol K, ΔG≠ = 76.69 kJ/mol; DMD-1a, ΔH≠ = 65.22 kJ/mol, ΔS≠ = -40.29 J/mol K, ΔG≠ = 101.38 kJ/mol; DMD-1s, ΔH≠ = 60.08 kJ/mol, ΔS≠ = -129.03 J/mol K, ΔG≠ = 98.58 kJ/mol; DHD- 7a, ΔH≠ = 56.11 kJ/mol, ΔS≠ = -113.72 J/mol K, ΔG≠ = 90.00 kJ/mol; DHD-7s; ΔH≠ = 50.67 kJ/mol, ΔS≠ = -120.58 J/mol K, ΔG≠= 88.49 kJ/mol; DHD-8a, ΔH≠ = 48.49 kJ/mol, ΔS≠= -114.22 J/mol K, ΔG≠= 82.51 kJ/mol; DHD-8s, ΔH≠ = 72.97 kJ/mol, ΔS≠ = -104.52 J/mol K, ΔG≠= 106.57 kJ/mol; anti, exo-1, ΔH≠ = 49.04 kJ/mol , ΔS≠ = -121.80 J/mol K, ΔG≠ = 85.35 kJ/mol; syn,exo-1, ΔH≠ = 47.86 kJ /mol, ΔS≠ = -122.84 J/mol K, ΔG≠ = 82.84 kJ/mol; anti endo-1, ΔH≠ = 54.77 kJ /mol, ΔS≠= -120.96 J/mol K, ΔG≠= 90.88 kJ/mol; syn, endo-1, ΔH≠= 48.74 kJ/mol, ΔS≠ = -132.26 J/mol K, ΔG≠ = 88.20 kJ/mol.
36. Manuscript in preparation.
37. Gandolfi, R.; Tonoletti, G.; Rastelli A.; Bagatti, M. J. Org. Chem. 1993, 58, 6038-6048.
38. Owing to excessive CPU time requirement, frequencies were not calculated for the Tss
39. For example, the energy required to deform the cyclic sulfite (o)-7 from ground state geometry to geometry it assumes in the DHD-7s and DHD-7a TSs is 6.98 kJ/mol and 7.88 kJ/mol, respectively. Thus, the out-of-plane deformation effect gives rise to an electronic energy stabilization by 0.9 kJ/mol for the DHD-7s over the DHD-7a.