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Unique Steric Effect of Geminal Bis(silane) To Control the High Exo-selectivity in Intermolecular Diels-Alder Reaction.
- Source :
-
Journal of the American Chemical Society [J Am Chem Soc] 2016 Feb 17; Vol. 138 (6), pp. 1877-83. Date of Electronic Publication: 2016 Feb 04. - Publication Year :
- 2016
-
Abstract
- The unique steric effect of geminal bis(silane) [(R3Si)2CH] allows an exo-selective intermolecular Diels-Alder reaction of geminal bis(silyl) dienes with α,β-unsaturated carbonyl compounds. The approach shows good generality to form ortho-trans cyclohexenes in good yields with high exo-selectivity and high enantioselectivity in some asymmetric cases. The excellent exo-stereocontrol aptitude of (R3Si)2CH group is highlighted by comparing with R3SiCH2 and R3Si groups, which leads to endo-selectivity predominantly. The conformational analysis of dienes suggests that (R3Si)2CH group effectively shields both sides of the diene moiety, ensuring the desired exo-selectivity. Moreover, the geminal bis(silane) can be further functionalized to transform the resulting ortho-trans cycloadducts into useful synthons, which makes the approach hold great potential for organic synthesis.
Details
- Language :
- English
- ISSN :
- 1520-5126
- Volume :
- 138
- Issue :
- 6
- Database :
- MEDLINE
- Journal :
- Journal of the American Chemical Society
- Publication Type :
- Academic Journal
- Accession number :
- 26799581
- Full Text :
- https://doi.org/10.1021/jacs.5b09689