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Synfacts 2013; 9(1): 0074
DOI: 10.1055/s-0032-1317773
DOI: 10.1055/s-0032-1317773
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
Asymmetric Synthesis of α,β-Thioepoxy Carbonyls by Rhodium Catalysis
Authors
Cano I, Gómez-Bengoa E, Landa A, Maestro M, Mielgo A, Olaizola I, Oiarbide M, Palomo C * Universidad del País Vasco, San Sebastián and Universidade da Coruña, Spain
N-(Diazoacetyl)oxazolidin-2-thiones as Sulfur-Donor Reagents: Asymmetric Synthesis of Thiiranes from Aldehydes.
Angew. Chem. Int. Ed. 2012;
51: 10856-10860
N-(Diazoacetyl)oxazolidin-2-thiones as Sulfur-Donor Reagents: Asymmetric Synthesis of Thiiranes from Aldehydes.
Angew. Chem. Int. Ed. 2012;
51: 10856-10860
Further Information
Publication History
Publication Date:
17 December 2012 (online)
Significance
Stereoselective formation of C–S bonds is a difficult yet important challenge. This report describes the use of diazo thiianes as intramolecular sulfur-donor reagents. Under rhodium catalysis, reaction with aldehydes forms thiiranes with high selectivity.
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Comment
Computational studies indicate formation of thiocarbonyl ylide intermediate A. Reaction with an aldehyde yields a tricyclic adduct, with preferential formation of anti,exo-product B by 0.8–1.2 kcal/mol, which collapses to the cis product by an SN2 reaction. However, when the aryl substituent is anisyl, the trans product forms by an SN1 mechanism.
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