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Synfacts 2013; 9(1): 0052
DOI: 10.1055/s-0032-1317749
DOI: 10.1055/s-0032-1317749
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
Rhodium-Catalyzed Asymmetric Vinylogous Addition to Vinyldiazoacetates
Weitere Informationen
Publikationsverlauf
Publikationsdatum:
17. Dezember 2012 (online)
Key words
rhodium - vinylogous addition - silyl enol ethers - siloxyvinyldiazoacetate - chiral tetracarboxylate ligands
Significance
A rhodium-catalyzed asymmetric vinylogous addition of silyl enol ethers to siloxyvinyldiazoacetates is reported. Depending on the sterics of the substituents on the substrate, this method can access cyclopentenones 2 or alkynoates 3 with high yield and excellent enantioselectivity.
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Comment
The use of (Z)-silyl enol ethers is critical in achieving the observed enantioselectivity. In the proposed mechanism, vinylogous adduct 5 can undergo a stereoselective 1,4-silyoxy shift to form 3. Bulkier R1 groups favor the aldol reaction to form formal [3+2] adduct 6, which in one pot, in acid, can afford 2.
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