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Chemo- and stereoselective six-membered oxonium ylide formation–[2,3]-sigmatropic rearrangement of 2-diazo-3-ketoesters with dirhodium(II) catalyst and its application to the synthesis of (+)-tanikolide
- Source :
- Tetrahedron. 75:2436-2445
- Publication Year :
- 2019
- Publisher :
- Elsevier BV, 2019.
-
Abstract
- Dirhodium(II)-catalyzed oxonium ylide formation–[2,3]-sigmatropic rearrangement of 6-allyloxy-2-diazo-3-ketoesters possessing a C-6 substituent is described. The reaction of 6-alkyl- or 6-aryl-substituted 6-allyloxy-2-diazo-3-ketoesters with a catalytic amount of Rh2(S-PTTL)4 proceeded in a chemoselective and stereoselective manner to provide 6-substituted 2-allyl-3-oxotetrahydropyran-2-carboxylates in good yields and with high diastereoselectivities. To demonstrate the utility of this sequential reaction, we conducted the total synthesis of (+)-tanikolide, in which the construction of the δ-lactone skeleton was achieved by employing a 2-iodobenzamide-catalyzed oxidative cleavage of tetrahydropyran-2-methanol.
- Subjects :
- chemistry.chemical_classification
010405 organic chemistry
2,3-sigmatropic rearrangement
Organic Chemistry
Substituent
Total synthesis
010402 general chemistry
01 natural sciences
Biochemistry
Medicinal chemistry
0104 chemical sciences
Catalysis
chemistry.chemical_compound
chemistry
Ylide
Drug Discovery
Diazo
Stereoselectivity
Oxonium ion
Subjects
Details
- ISSN :
- 00404020
- Volume :
- 75
- Database :
- OpenAIRE
- Journal :
- Tetrahedron
- Accession number :
- edsair.doi...........a4c461152ee3da31063c92528e68457d