کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
1348550 980359 2006 11 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Studies on the structure–enantioselectivity relationships in the catalytic asymmetric intramolecular cyclopropanation reaction of α-diazo-β-keto sulfones possessing a methyl-substituted phenyl group
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی معدنی
پیش نمایش صفحه اول مقاله
Studies on the structure–enantioselectivity relationships in the catalytic asymmetric intramolecular cyclopropanation reaction of α-diazo-β-keto sulfones possessing a methyl-substituted phenyl group
چکیده انگلیسی

This manuscript describes studies on structure–enantioselectivity relationships in the catalytic asymmetric intramolecular cyclopropanation (IMCP) reaction of α-diazo-β-keto sulfones possessing a methyl-substituted phenyl group. Enantioselectivity of the IMCP reaction of the α-diazo-β-keto sulfones was varied by the position of a methyl group on the phenyl group in the substrate, and the 2,3-dimethylphenyl sulfone 11h provided the product 12h in 95% yield with 93% ee. This yield is superior to that of the substrate with a mesityl sulfone 11b, and the product 12h is useful because alkylation of its cyclopropane-opened β-keto sulfone derivative 15h provides the C-alkylated product as a major product.

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(1R,5R)-1-(2-Methylphenylsulfonyl)bicyclo[3.1.0]hexan-2-oneC13H14O3SEe = 86%[α]D25 = −35.4 (c 1.00, CHCl3)Source of chirality: catalytic asymmetric intramolecular cyclopropanationAbsolute configuration: (1R,5R)

(1R,5R)-1-(3-Methylphenylsulfonyl)bicyclo[3.1.0]hexan-2-oneC13H14O3SEe = 77%[α]D26 = −35.8 (c 1.50, CHCl3)Source of chirality: catalytic asymmetric intramolecular cyclopropanationAbsolute configuration: (1R,5R)

(1R,5R)-1-(4-Methylphenylsulfonyl)bicyclo[3.1.0]hexan-2-oneC13H14O3SEe = 69%[α]D28 = −25.2 (c 0.75, CHCl3)Source of chirality: catalytic asymmetric intramolecular cyclopropanationAbsolute configuration: (1R,5R)

(1R,5R)-1-(2,3-Dimethylphenylsulfonyl)bicyclo[3.1.0]hexan-2-oneC14H16O3SEe = >99%[α]D26 = −37.2 (c 1.02, CHCl3)Source of chirality: catalytic asymmetric intramolecular cyclopropanationAbsolute configuration: (1R,5R)

(1R,5R)-1-(2,5-Dimethylphenylsulfonyl)bicyclo[3.1.0]hexan-2-oneC14H16O3SEe = 82%[α]D28 = −43.0 (c 1.05, CHCl3)Source of chirality: catalytic asymmetric intramolecular cyclopropanationAbsolute configuration: (1R,5R)

(1R,5R)-1-(2,6- Dimethylphenylsulfonyl)bicyclo[3.1.0]hexan-2-oneC14H16O3SEe = 91%[α]D28 = −50.0 (c 1.25, CHCl3)Source of chirality: catalytic asymmetric intramolecular cyclopropanationAbsolute configuration: (1R,5R)

(1R,5R)-1-(3,4-Dimethylphenylsulfonyl)bicyclo[3.1.0]hexan-2-oneC14H16O3SEe = 72%[α]D28 = −42.3 (c 1.09, CHCl3)Source of chirality: catalytic asymmetric intramolecular cyclopropanationAbsolute configuration: (1R,5R)

(1R,5R)-1-(3,5-Dimethylphenylsulfonyl)bicyclo[3.1.0]hexan-2-oneC14H16O3SEe = 62%[α]D28 = −41.0 (c 1.37, CHCl3)Source of chirality: catalytic asymmetric intramolecular cyclopropanationAbsolute configuration: (1R,5R)

(1R,2R)-[2-(2,3-Dimethylbenzenesulfonyl)-3-oxocyclopentyl]acetonitrileC15H17NO3SEe = 93%[α]D25 = −33.0 (c 1.15, CHCl3)Source of chirality: catalytic asymmetric intramolecular cyclopropanationAbsolute configuration: (1R,2R)

(R)-(3-Oxocyclopentyl)acetonitrileC7H9NOEe = >99%[α]D24 = −70.1 (c 1.20, CHCl3)Source of chirality: catalytic asymmetric intramolecular cyclopropanationAbsolute configuration: (R)

(R)-[2-(2,3-Dimethylbenzenesulfonyl)-3-methoxy-2-cyclopentenyl]acetonitrileC16H19NO3SEe = 93%[α]D25 = −17.9 (c 0.72, CHCl3)Source of chirality: catalytic asymmetric intramolecular cyclopropanationAbsolute configuration: (R)

(R)-[2-(2,3-Dimethylbenzenesulfonyl)-3-(2-propynyloxy)-2-cyclopentenyl]acetonitrileC18H19NO3SEe = 93%[α]D25 = −11.2 (c 0.94, CHCl3)Source of chirality: catalytic asymmetric intramolecular cyclopropanationAbsolute configuration: (R)

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Tetrahedron: Asymmetry - Volume 17, Issue 20, 6 November 2006, Pages 2896–2906
نویسندگان
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