benzyl 2,3-di-O-benzyl-4,6-O-sulfuryl-β-D-galactopyranoside | 220449-92-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: benzyl 2,3-di-O-benzyl-4,6-O-sulfuryl-β-D-galactopyranoside
• 英文别名: (4aR,6R,7R,8R,8aS)-6,7,8-tris(phenylmethoxy)-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3,2]dioxathiine 2,2-dioxide
• CAS: 220449-92-3
• 化学式: C₂₇H₂₈O₈S
• 分子量: 512.581
• InChiKey: SPPUCFINKKUSAO-LXSUACKSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  36
• 可旋转键数：
  9
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  97.9
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  benzyl 2,3-di-O-benzyl-4,6-O-sulfuryl-β-D-galactopyranoside 在 palladium on activated charcoal 六氟异丙醇 、 氢气 作用下， 以 甲醇 为溶剂， 20.0~70.0 ℃ 、101.33 kPa 条件下， 反应 66.0h， 生成 4-O-sulfoxy-6-deoxy-6-[1,4-dideoxy-1,4-episulfoniumylidene-D-arabinitol]-α-D-galactopyranose inner salt
  参考文献：
  名称：

  Synthesis of Sulfonium Sulfate Analogues of Disaccharides and Their Conversion to Chain-Extended Homologues of Salacinol: New Glycosidase Inhibitors

  摘要：

  [graphics]Four chain extended homologues of salacinol, a naturally occurring glycosidase inhibitor, were prepared for evaluation as inhibitors of glucosidase enzymes involved in the breakdown of carbohydrates. The syntheses involved the reactions of 1,4-anhydro-2,3,5-tri-O-benzyl-4-thiO-D-arabinitol with cyclic sulfate derivatives of different monosaccharides. Debenzylation of the products afforded the novel sulfonium sulfate derivatives Of D-glucose, D-galactose, D-arabinose, and D-Xylose that are of interest in their own right as glycosidase inhibitors. Reduction to the corresponding alditols then afforded the homologues of salacinol containing polyhydroxylated, acyclic chains of 5- and 6-carbons, differing in stereochemistry at the stereogenic centers. Three of the chain-extended homologues inhibited recombinant human maltase glucoamylase, one of the key intestinal enzymes involved in the breakdown of glucose oligosaccharides in the sinall intestine, with K-i values in the low microinolar range, of approximately the saine inagnitude as salacinol, thus providing lead candidates for the treatment of Type 2 diabetes.

  DOI：

  10.1021/jo052252u
• 作为产物：
  描述：

  苄基2,3-二-O-苄基-beta-D-吡喃半乳糖苷 在 ruthenium trichloride 、 sodium periodate 、 氯化亚砜 、 三乙胺 作用下， 以 四氯化碳 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 4.5h， 生成 benzyl 2,3-di-O-benzyl-4,6-O-sulfuryl-β-D-galactopyranoside
  参考文献：
  名称：

  Ring Opening of Benzyl β-D-Galactoside Cyclic Sulfates into Galactose Monosulfates. New Access to 6-Deoxy-Galacto-Hex-5-Enopyranoside and 4-Deoxy-3-Ketogalactopyranoside.

  摘要：

  The behavior of 3,4- and 4,6-cyclic sulfates derived from benzyl 2,6- and 2,3-di-O-benzyl-beta-D-galactopyranosides toward hydrolysis has been studied using aqueous sodium hydroxide under various conditions. Starting from benzyl 2,6-di-0-benzyl-3,4-O-sulfuryl-beta-D-galactopyranoside (5), the reaction with aq NaOH in THF gave both 3- and 4-monosulfates 7 and 8 (83%, in 68:32 ratio), while the reaction in DMF led unexpectedly to the 4-deoxy-3-keto derivative 10 in 77% yield after acidic hydrolysis of the intermediate enolester 9. On the other hand, when benzyl 2,3-di-O-benzyl-4,6-O-sulfuryl-beta-D-galactopyranoside (6) was treated with aq NaOH in THF, a mixture of benzyl 2,3-di-O-benzyl-6-deoxy-4-O-(sodium sulfonato)-alpha-L-arabino-hex-5-enopyranoside (11) and benzyl 2,3-di-O-benzyl-4-deoxy-6-O-(sodium sulfonato)-alpha-L-threo-hex-4-enopyranoside (12) (in 65:35 ratio) was obtained in 93% yield, giving a new and rapid access to 11, a potential precursor of L-sugars derivatives. Alternatively, BzONBu(4), gave a regiospecific opening reaction of 6 and led to the 6-O-benzoate 4-O-sulfate derivative (13) in excellent yield.

  DOI：

  10.1080/07328300008544080

文献信息

• US8389565B2
  申请人：——

  公开号：US8389565B2

  公开（公告）日：2013-03-05
• Ring Opening of Benzyl β-D-Galactoside Cyclic Sulfates into Galactose Monosulfates. New Access to 6-Deoxy-<i>Galacto</i>-Hex-5-Enopyranoside and 4-Deoxy-3-Ketogalactopyranoside.
  作者：Franck Dagron、André Lubineau

  DOI：10.1080/07328300008544080

  日期：2000.1

  The behavior of 3,4- and 4,6-cyclic sulfates derived from benzyl 2,6- and 2,3-di-O-benzyl-beta-D-galactopyranosides toward hydrolysis has been studied using aqueous sodium hydroxide under various conditions. Starting from benzyl 2,6-di-0-benzyl-3,4-O-sulfuryl-beta-D-galactopyranoside (5), the reaction with aq NaOH in THF gave both 3- and 4-monosulfates 7 and 8 (83%, in 68:32 ratio), while the reaction in DMF led unexpectedly to the 4-deoxy-3-keto derivative 10 in 77% yield after acidic hydrolysis of the intermediate enolester 9. On the other hand, when benzyl 2,3-di-O-benzyl-4,6-O-sulfuryl-beta-D-galactopyranoside (6) was treated with aq NaOH in THF, a mixture of benzyl 2,3-di-O-benzyl-6-deoxy-4-O-(sodium sulfonato)-alpha-L-arabino-hex-5-enopyranoside (11) and benzyl 2,3-di-O-benzyl-4-deoxy-6-O-(sodium sulfonato)-alpha-L-threo-hex-4-enopyranoside (12) (in 65:35 ratio) was obtained in 93% yield, giving a new and rapid access to 11, a potential precursor of L-sugars derivatives. Alternatively, BzONBu(4), gave a regiospecific opening reaction of 6 and led to the 6-O-benzoate 4-O-sulfate derivative (13) in excellent yield.
• Synthesis of Sulfonium Sulfate Analogues of Disaccharides and Their Conversion to Chain-Extended Homologues of Salacinol: New Glycosidase Inhibitors
  作者：Blair D. Johnston、Henrik H. Jensen、B. Mario Pinto

  DOI：10.1021/jo052252u

  日期：2006.2.1

  [graphics]Four chain extended homologues of salacinol, a naturally occurring glycosidase inhibitor, were prepared for evaluation as inhibitors of glucosidase enzymes involved in the breakdown of carbohydrates. The syntheses involved the reactions of 1,4-anhydro-2,3,5-tri-O-benzyl-4-thiO-D-arabinitol with cyclic sulfate derivatives of different monosaccharides. Debenzylation of the products afforded the novel sulfonium sulfate derivatives Of D-glucose, D-galactose, D-arabinose, and D-Xylose that are of interest in their own right as glycosidase inhibitors. Reduction to the corresponding alditols then afforded the homologues of salacinol containing polyhydroxylated, acyclic chains of 5- and 6-carbons, differing in stereochemistry at the stereogenic centers. Three of the chain-extended homologues inhibited recombinant human maltase glucoamylase, one of the key intestinal enzymes involved in the breakdown of glucose oligosaccharides in the sinall intestine, with K-i values in the low microinolar range, of approximately the saine inagnitude as salacinol, thus providing lead candidates for the treatment of Type 2 diabetes.