Stereocontrolled synthesis of glycosidase inhibitors (+)-hyacinthacines A1 and A2. Issue 2 (15th February 2015)

• Record Type: Journal Article
• Authors: Veyron, Amaël; Reddy, Paidi Venkatram; Koos, Peter; Bayle, Alexandre; Greene, Andrew E.; Delair, Philippe
• Is Part Of: Tetrahedron, asymmetry. Volume 26:Issue 2/3(2015)
• Page Start: 85
• Page End: 94
• Publication Date: 2015-02-15
• Subjects: Asymmetry (Chemistry) -- Periodicals; 547.005
• DOI: 10.1016/j.tetasy.2014.12.002
• Languages: English
• ISSNs: 0957-4166

Abstract

Graphical abstract: Abstract: (+)-Hyacinthacines A1 and A2 have been prepared from an easily available, advanced intermediate. The non-chiral pool approach features a dichloroketene–enol ether [2+2] cycloaddition and a dihydroxylation or epoxidation as key stereoselective transformations. Abstract : (+)-Hyacinthacine A1 : C8 H15 NO3 [ α ]D 21 = +43.9 ( c 0.3, H2 O) Source of chirality: ( S )-(−)-Stericol Absolute configuration: (1 S, 2 R, 3 R, 7a R ) Abstract : (+)-Hyacinthacine A2 : C8 H15 NO3 [ α ]D 23 = +12.0 ( c 0.45, H2 O) Source of chirality: ( S )-(−)-Stericol Absolute configuration: (1 R, 2 R, 3 R, 7a R ) Abstract : (2 R, 3 R )- tert -Butyl 2-allyl-5-oxo-3-[( S )-1-(2, 4, 6-triisopropylphenyl)ethoxy]-pyrrolidine-1-carboxylate: C29 H45 NO4 [ α ]D 21 = −98.4 ( c 0.6, CHCl3 ) Source of chirality: ( S )-(−)-Stericol Absolute configuration: (2 R, 3 R ) Abstract : (1 R, 3 S, 7a R )-3-{[Dimethyl(phenyl)silyl]methyl}-hexahydro-1 H -pyrrolizin-1-ol: C16 H25 NOSi [ α ]D 21 = −45.0 ( c 0.91, CHCl3 ) Source of chirality: ( S )-(−)-Stericol Absolute configuration: (1 R, 3 S, 7a R ) Abstract : (5 S, 6 R, 7 S, 7a R )-6, 7-Dihydroxy-5-((dimethyl(phenyl)silyl)methyl)-hexahydropyrrolizin-3-one: C16 H23 NO3 Si [ α ]D 21 = −58.7 ( c 1.1, CHCl3 ) Source of chirality: ( S )-(−)-Stericol Absolute configuration: (5 S, 6 R, 7 S, 7a R ) Abstract : (5 S, 7 R, 7a R )-5-((Dimethyl(phenyl)silyl)methyl)-7-(( S )-1-(2, 4, 6-triisopropylphenyl)ethoxy)-hexahydro-1 H -pyrrolizin-3-one: C33 H49 NO2 Si [ α ]D 21 = −82.9 ( c 1.4, CHCl3 ) Source of chirality: ( S )-(−)-Stericol Absolute configuration: (5 S, 7 R, 7a R ) Abstract : (5 S, 7 R, 7a R )-5-((Dimethyl(phenyl)silyl)methyl)-7-hydroxy-hexahydro-1 H -pyrrolizin-3-one: C16 H23 NO2 Si [ α ]D 21 = −73.4 ( c 1.6, CHCl3 ) Source of chirality: ( S )-(−)-Stericol Absolute configuration: (5 S, 7 R, 7a R ) Abstract : (5 S, 7a R )-5-((Dimethyl(phenyl)silyl)methyl)-1, 2, 5, 7a-tetrahydropyrrolizin-3-one: C16 H21 NOSi [ α ]D 21 = −177.2 ( c 0.7, CHCl3 ) Source of chirality: ( S )-(−)-Stericol Absolute configuration: (5 S, 7a R ) Abstract : (5 R, 6 R, 7 S, 7a R )-6, 7-Dihydroxy-5-(hydroxymethyl)hexahydropyrrolizin-3-one: C8 H13 NO4 [ α ]D 21 = −49.9 ( c 0.7, CH3 OH) Source of chirality: ( S )-(−)-Stericol Absolute configuration: (5 S, 6 R, 7 S, 7a R ) Abstract : (1a R, 2 S, 6a R, 6b S )-2-((Dimethyl(phenyl)silylmethyl)-hexahydro-oxireno[2, 3- a ]pyrrolizin-4-one: C16 H21 NO2 [ α ]D 21 = −95.6 ( c 1.2, CHCl3 ) Source of chirality: ( S )-(−)-Stericol Absolute configuration: (1a R, 2 S, 6a R, 6b S ) Abstract : (5 S, 6 R, 7 R, 7a R )-6, 7-Dihydroxy-5-((dimethyl(phenyl)silyl)methyl)-hexahydropyrrolizin-3-one: C16 H23 NO3 Si [ α ]D 21 = −52.1 ( c 0.7, CHCl3 ) Source of chirality: ( S )-(−)-Stericol Absolute configuration: (5 S, 6 R, 7 R, 7a R ) Abstract : (5 R, 6 R, 7 R, 7a R )-6, 7-Dihydroxy-5-(hydroxymethyl)hexahydropyrrolizin-3-one: C8 H13 NO4 [ α ]D 23 = −46.3 ( c 1.2, MeOH) Source of chirality: ( S )-(−)-Stericol Absolute configuration: (5 R, 6 R, 7 R, 7a R )