[1,3], [3,3], and [3,5] sigmatropic rearrangement of esters are pseudopericyclic

Angewandte Chemie - International Edition

Volumn 38, Issue 1-2, 1999, Pages 189-193

  Birney, David M ^a   Xu, Xiaolian ^a   Ham, Sihyun ^a  

^a TEXAS TECH UNIVERSITY   (United States)

Author keywords

Ab initio calculations; Pericyclic reactions; Rearrangements

Indexed keywords

ARTICLE; CHEMICAL BOND; CHEMICAL REACTION; CONFORMATIONAL TRANSITION; MATHEMATICAL ANALYSIS; STRUCTURE ANALYSIS;

EID: 0033556194     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(sici)1521-3773(19990115)38:1/2<189::aid-anie189>3.0.co;2-v     Document Type: Article

References (31)

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16. B. Miller in Mechanisms of Molecular Migrations, Vol. 1 (Ed.: B. S. Thyagarajan), Interscience, New York, 1968, pp. 247-314; see in particular page 261. A radical mechanism was suggested instead. There is evidence for radical pathways in the formation of minor products in acetate eliminations: B. Shi, Y. Ji, H. A. Dabbagh, B. H. Davis, J. Org. Chem. 1994, 59, 845-849.)
17. [12] The relative energies discussed in the text are from the highest calculated level shown in Table 1. Full geometries and absolute energies are available in the supporting information.
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21. A Nazarov-type cyclization to 3 would be possible in analogy to 10, but would be disfavored by strain.
22. 2 is a consequence of the weak interaction between the two oxygen lone pairs.
23. [16] The situation here is somewhat different in that the three HOMOs shown in Figure 3 are essentially noninteracting. Furthermore, the [3,3] and [3,5] rearrangements of 4 are both orbital symmetry allowed.
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28. These structures were only optimized at the RHF/6-31G ** level.
29. s symmetry for this rearrangement has been calculated,[5] but no TS was reported. The three lowest energy conformations of 1 were recalculated (1a-c in this work correspond to 5, 3, and 1, respectively, in ref. [5]).
30. MP4/6-31G** ± ZPE.[5]
31. E. M. Engler, J. D. Andose, P. von R. Schleyer, J. Am. Chem. Soc. 1973, 95, 8005-8025.