Stereoelectronic control of facial selectivity in the Diels-Alder cycloaddition of sterically unbiased 5,5-diarylcyclopentadienes
β Scribed by Halterman, Ronald L.; McCarthy, Bridget A.; McEvoy, Marjorie A.
- Book ID
- 120871487
- Publisher
- American Chemical Society
- Year
- 1992
- Tongue
- English
- Weight
- 714 KB
- Volume
- 57
- Category
- Article
- ISSN
- 0022-3263
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A study of t he p i-fa c ial sel e ctivit y o f the Diels -Alder reaction of N -ben~oyl 5methox ycarbonyl-2-a~a-oxabi cyclo[2 .2.2]oct-4-ene, a rigid electron de f i cie nt dienoph i l e bearing t wo allylic axial heteroat om subst ituents, with I -me thoxy-3-trimet h ylsil yl oxybut adi ene , a r e
p-Facial selectivity in Diels-Alder reactions of cyclopentadienes having C( O)YR substituents at the 5-positions was predicted on the basis of the orbital mixing rule and was substantiated experimentally. The selectivity was disclosed to be highly dependent on the relative orbital energy between p H