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Volumn 63, Issue 15, 1998, Pages 5216-5227

Origins of Stereocontrol in the [2 + 2] Cycloaddition between Achiral Ketenes and Chiral α-Alkoxy Aldehydes. A Pericyclic Alternative to the Aldol Reaction

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EID: 0000096837     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9806512     Document Type: Article
Times cited : (21)

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    • note
    • 3-hybridized oxygen atom of the aldehyde could be more important than solvent effects. To check this hypothesis, we have optimized the complex between ammonium cation and hydroxyacetaldehyde. We have found that at the HF/6-31G* level the cation forms a hydrogen bond with the hydroxylic oxygen. However, at the B3LYP/6-31G* level, hydrogen bonding occurs through the oxygen of the carbonyl group. These interactions should be lower at the TS and with bulkier substituents. The electrostatic effect, if any, should be not very directional in character and will not affect significantly the stereochemical outcome. (Equation Presented)
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    • note
    • This TS has been calculated previously at other theoretical levels (see refs 16-18). Its main geometrical features at the B3LYP/6-31G* level are the following (bond distances are given in Å and numbers in parentheses correspond to the bond indices): (Equation Presented)
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    • As we have previously reported, in this reaction the magnitudes of the activation energies are underestimated at the MP2/6-31G* level (see ref 16). Probably, this deficiency can be extended to the B3LYP/6-31G* level. For recent studies on this problem, see: (a) Fabian, W. M. F.; Kollenz, G. J. Org. Chem. 1997, 62, 8497. (b) Durant, J. L. Chem. Phys Lett. 1996, 256, 595. (c) Glukhovtsev, M. N.; Bach, R. D.; Pross, A.; Radom, L. Chem. Phys. Lett. 1996, 260, 558.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.