Competition between peroxy acid oxygens as hydrogen bond acceptors in B3LYP transition structures for epoxidations of allylic alcohols with peroxyformic acid

Journal of Organic Chemistry

Volumn 64, Issue 11, 1999, Pages 3853-3860

  Freccero, Mauro ^a   Gandolfi, Remo ^a   Sarzi Amadè, Mirko ^a   Rastelli, Augusto ^b  

^a UNIVERSITY OF PAVIA   (Italy)

^b UNIVERSITY OF MODENA AND REGGIO EMILIA   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL; ALLYL COMPOUND; FORMIC ACID DERIVATIVE;

ARTICLE; CHEMICAL MODIFICATION; CHEMICAL STRUCTURE; CONFORMATIONAL TRANSITION; HYDROGEN BOND; MOLECULAR DYNAMICS; MOLECULAR INTERACTION; MOLECULAR STABILITY; PEROXIDATION; PHYSICAL CHEMISTRY;

EID: 0033612229     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo981743u     Document Type: Article

References (39)

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8. (b) For an excellent treatise on hydrogen bonding, see: Jeffrey, J. A. Introduction to hydrogen bonding; University Press: Oxford, 1997.
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17. 3-hybrid atomic orbitals) while in G a MO description of lone pairs is used.
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25. Tomasi, J.; Persico, M.Chem. Rev. 1997, 94, 2027.
26. 8 moiety and the olefin substituent with the highest Cahn-Ingold-Prelog priority are on the same (opposite) side.
27. 8 fragment is rotated away from the OH (allylic) group (γ = 121°). At the B3LYP/6-31G* level, the electronic energy (free enthalpy) of this TS is higher by 3.72 kcal/ mol (2.89 kcal/mol) with respect to 3b.
28. (b) To date we were not able to locate, for systems under study, TSs in which the peroxy acid is the hydrogen bond donor and the allylic alcohol the hydrogen bond acceptor (this interaction has been advanced as the facial selectivity controlling factor in the epoxidation with highly acidic peroxy acids by McKittrick, B. A.; Ganem, B. Tetrahedron Lett. 1985, 26, 4895); however, see: Fehr, C. Angew. Chem., Int. Ed. Engl. 1998, 37, 2407.
29. (b) To date we were not able to locate, for systems under study, TSs in which the peroxy acid is the hydrogen bond donor and the allylic alcohol the hydrogen bond acceptor (this interaction has been advanced as the facial selectivity controlling factor in the epoxidation with highly acidic peroxy acids by McKittrick, B. A.; Ganem, B. Tetrahedron Lett. 1985, 26, 4895); however, see: Fehr, C. Angew. Chem., Int. Ed. Engl. 1998, 37, 2407.
30. 11 the electronic activation energy for their TSs (our 3a and 3b) without specifying with respect to which conformer it was calculated. Their values can be reproduced by using as reactant the propenol conformer 1e.
31. Freccero, M.; Gandolfi, R.; Sarzi-Amadè M.; Rastelli, A. Unpublished results.
32. 2 dihedral angle. Thus, both exo and endo TSs exhibit three conformations that roughly correspond to the a, c, and d conformations of the starting allylic alcohols.
33. 3a
34. Also at the B3LYP/6-311+G** level TS 4b is favored over 3b by entropy factors (2.2 eu).
35. Solvation energies calculated with the AMSOL method (in cyclohexane, ∈ = 2.02) confirm the results of the Tomasi method (in benzene, ∈ = 2.30). See Tables 4 and 13 of the Supporting Information. After solvent effect is added to the B3LYP/6-31G* (B3LYP/6-311G**) data, the relative free enthalpies for 4b, 3b, 4a, 3a, 6a, and 5a are as follows: -0.16, 0.00, 0.34, 1.83, 1.97, 2.70 (-0.64, 0.00, 0.17, 1.87, 1.66, 2.74) kcal/mol.
36. 3 dihedral angle in syn,exo-4a and syn,exo-4b exhibits a very similar value to that in the corresponding TSs for dimethyldioxirane epoxidation of propenol (i.e., 135.0° vs 135.9° and 16.0° vs 20.8°, respectively).
37. 29 by suggesting a conformation of type b (with O-C-C=C ≈ 30°) wherein the alkene hydroxylic proton hydrogen bonds the proximal peroxo oxygen of the peroxy acid. In both models the peroxy acid proton hydrogen bonds the homoallylic ether.
38. Johnson, M. R.; Kishi, Y. Tetrahedron Lett. 1979, 4347.
39. A perfect "perpendicular" spiro geometry with both γ = 90° and δ = 90° is intrinsically favored in epoxidation with peroxy acid. However, the system seems to resist more to deviate from δ = 90° than from γ = 90°. Actually deviations of δ values from 90° are less than 7° for all the TSs reported in Table 2. In the case of γ deviations from 90° are less than ∼10° for Sharpless-like exo TSs, but much larger distortions (even by >30°) were observed for endo orientations. That is, TSs of peroxy acid epoxidation exhibit a high flexibility as far as the γ parameter is concerned: large deviations from 90°, which allow the system to accommodate steric interactions and to strengthen hydrogen bonding, do not give rise to prohibitive energy increase. The potential energies surface is flat in the region of the TS with respect to the motion described by γ.