Back to Search
Start Over
Diastereoselective rhodium(II)-catalyzed sulfonium ylide formation-[2,3]-sigmatropic rearrangement reaction of chiral non-racemic allylic sulfides
- Source :
- Tetrahedron: Asymmetry. 14:897-909
- Publication Year :
- 2003
- Publisher :
- Elsevier BV, 2003.
-
Abstract
- The tandem sulfonium ylide formation-[2,3]-sigmatropic rearrangement reaction of chiral non-racemic secondary allylic sulfides, (E)-9 and (Z)-10, is found to proceed with high diastereocontrol. The C-5 stereocenter bearing the sulfide group is essential for high diastereoselectivity in the reaction. Transition state conformers are proposed to explain the high diastereoselectivity in the formation of the diastereomeric products, 18a and 18b. The method is applied to the synthesis of (R)-4-(4-chlorophenyl)-2-butyrolactone. Modest enantioselectivity (63% ee) was achieved and this is attributed to partial racemization during the formation of the secondary allylic sulfide 22.
- Subjects :
- chemistry.chemical_classification
Allylic rearrangement
Stereochemistry
Sulfonium
2,3-sigmatropic rearrangement
Organic Chemistry
Diastereomer
Catalysis
Stereocenter
Inorganic Chemistry
chemistry.chemical_compound
chemistry
Ylide
Rearrangement reaction
Physical and Theoretical Chemistry
Racemization
Subjects
Details
- ISSN :
- 09574166
- Volume :
- 14
- Database :
- OpenAIRE
- Journal :
- Tetrahedron: Asymmetry
- Accession number :
- edsair.doi...........4b0a2d745b852c348245caceb38aa9c0