Chiral induction in photochemical reactions - 15.: Detection of stereoelectronic effects by temperature dependent measurements of the diastereoselectivity in the photosensitized [2+2]-cycloaddition
作者： Norbert Hoffmann , Helmut Buschmann , Gerhard Raabe , Hans-Dieter Scharf
DOI: 10.1016/S0040-4020(01)89419-9
关键词: Steric effects 、 Electronic effect 、 Enone 、 Alkoxy group 、 Photochemistry 、 Cycloaddition 、 Chemistry 、 Aliphatic compound 、 Eyring equation 、 Substituent
摘要: Abstract The mechanism of the diastereoselection in photosensitized[2 + 2]-cycloaddition reaction ethylene to 5-alkoxy-2(5H)-furanones is investigated. dependence product ratio on temperature as well structural features enone system measured. structure dependent activation parameter differences (ΔΔH≠,ΔΔS≠) obtained by this method (modified Eyring plot) are used a tool characterize stereoelectronic factors, which responsible for diastereoselection. In detail these factors involve: pyramidalization β-carbon, homoanomeric effect, and steric requirements alkoxy substituent relaxed (3ππ*)-excited furanones.
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sci-hub.se 参考文章(134)
Nicolaos Demetrios Epiotis, Theory of Organic Reactions ,(1978)
J. D. Coyle, H. A. J. Carless, Photochemistry in organic synthesis Royal Society of Chemistry. ,(1986)
Kinetics and spectroscopy of carbenes and biradicals Plenum Press. ,(1990) , 10.1007/978-1-4899-3707-0
A. Pross, The Reactivity—Selectivity Principle and its Mechanistic Applications Advances in Physical Organic Chemistry. ,vol. 14, pp. 69- 132 ,(1977) , 10.1016/S0065-3160(08)60108-2
Joachim Gersdorf, Jochen Mattay, Helmut Goerner, Photoreactions of biacetyl, benzophenone, and benzil with electron-rich alkenes Journal of the American Chemical Society. ,vol. 109, pp. 1203- 1209 ,(1987) , 10.1021/JA00238A033
Helmut Duddeck, Substituent Effects on 13C Chemical Shifts in Aliphatic Molecular Systems. Dependence on Constitution and Stereochemistry Topics in Stereochemistry. ,vol. 16, pp. 219- 324 ,(2007) , 10.1002/9780470147252.CH4
George S. Hammond, A Correlation of Reaction Rates Journal of the American Chemical Society. ,vol. 77, pp. 334- 338 ,(1955) , 10.1021/JA01607A027
Steven C. Freilich, Kevin S. Peters, Observation of the 1,4 biradical in the Paterno-Buchi reaction Journal of the American Chemical Society. ,vol. 103, pp. 6255- 6257 ,(1981) , 10.1021/JA00410A062
David J. Maradyn, Leiv K. Sydnes, Alan C. Weedon, Origin of the regiochemistry in the photochemical cycloaddition reaction of 2-cyclopentenone with allene: Trapping of triplet 1,4-biradical intermediates with hydrogen selenide☆ Tetrahedron Letters. ,vol. 34, pp. 2413- 2416 ,(1993) , 10.1016/S0040-4039(00)60429-X
Chan Moon Chung, Masaki Hasegawa, "Kaleidoscopic" photoreaction behavior of alkyl 4-[2-(4-pyridyl)ethenyl]cinnamate crystals: a crystalline linear high polymer from the methyl ester, an "absolute" asymmetric reaction of the ethyl ester, and two types of dimer formation from the propyl ester Journal of the American Chemical Society. ,vol. 113, pp. 7311- 7316 ,(1991) , 10.1021/JA00019A031