Perturbed Pericyclic Reactions: Stereochemical Consequences of Heterosubstitution. A Qualitative Mechanistic Model Based on the Nonpreservation of Orbital Topology

Journal of Organic Chemistry

Volumn 45, Issue 7, 1980, Pages 1341-1344

  Snyder, James P ^a  

^a UNIVERSITY OF COPENHAGEN   (Denmark)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0003222465     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo01295a046     Document Type: Article

References (48)

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27. Energy barriers (ΔE*) for the incremental, unoptimized closure of cis dienes 1 to the four-membered ring 2 are as follows (X, ΔE* in kcal/mol): CH2, 55 (con) (vs. MINDO-3,23,24b 50; STO-3G,27 67; ab initio, 24b,25 60; ab initio Cl,24b,25 56); endo-NH, 45 (con), 48 (dis); NH2+, 27 (con), 29 (dis); O, 44; endo-OH+, 29 (con, dis); S, 48; endo-SH+, 36 (con), 37 (dis). As is usual for single-determinant calculations, the stability of the four-membered rings is overestimated, leading to an exothermic ring closure in most cases [X, ΔE_reac (1 → 2) in kcal/mol]: CH2,-10 (vs. O.5 to-20 kcal/mol by other methods23,24a,27,28b and +9 kcal/mol by experiment28b); endo-NH,-17; MH2+,-14; O,-28; endo-OH+,-23; S,-2; endo-SH+, 10 kcal/mol.
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31. Strictly speaking when a system is devoid of symmetry, all MO's are characterized by the same point group, C. Operation of the noncrossing rule2,30 then guarantees that all filled MO's transform within the bonding/nonbonding manifold; i.e., “forbidden” reactions are forbidden since avoided HOMO-LUMO crossings are strongly avoided (e.g., lbg/ 2b-g). However, for near-symmetric pericyclic processes, HOMOLUMO crossings are only nearly avoided, and a significant energy gap between “allowed” and “forbidden” paths results (e.g., 3b,c/4b,c).
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44. The lone-pair electrons for cases such as lb,e,g might conceivably alter the electronic course of the reaction by coverting the pericyclic transition state into a pseudopericyclic one.39 Careful optimization of the lb → 2b pathway by means of PRDDO-ST calculations27,40'41 has permitted elimination of the latter role for the nitrogen lone pair.
45. J. A. Ross, R. P. Seiders, and D. M. Lemal, J. Am. Chem. Soc., 98,4325 (1976); C. H. Bushweller, J. A. Ross, and D. M. Lemal, The lone-pair electrons for cases such as lb,e,g might conceivably alter the electronic course of the reaction by coverting the pericyclic transition state into a pseudopericyclic one.39 Careful optimization of the lb → 2b pathway by means of PRDDO-ST calculations27,40'41 has permitted elimination of the latter role for the nitrogen lone pair., 99, 629 (1977).
46. J. P. Snyder and T. A. Halgren, J. Am. Chem. Soc., in press.
47. J. P. Snyder, D. Crans, and T. A. Halgren, unpublished work.
48. Cf. H. Kloosterziel, J. A. A. van Drunen, and P. Galama, Chem. Commun., 885 (1969); H Kloosterziel and J. A. A. van Drunen, Reel. Trav. Chim. Pays-Bas, 89, 667 (1970); M. P. Doyle, J. G. Kalmbacher, W. Wiereng, and J. E. Deboer, Tetrahedron Lett., 1455 (1974); L. E. Overman and M. Kakimoto, J. Am. Chem. Soc., 101, 1310 (1979); H. Irie, I. Katayama, and Y. Mizuno, Heterocycles, 12, 771 (1979); T. Kusumi, K. Yoneda, and H. Kakisawa, Synth. Commun., 221 (1979).