diethyl C-(3,4,6-tri-O-benzyl-α-D-arabino-hexosulopyranosyl)methanephosphonate | 172223-10-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: diethyl C-(3,4,6-tri-O-benzyl-α-D-arabino-hexosulopyranosyl)methanephosphonate
• 英文别名: diethyl (((2S,4S,5R,6R)-4,5-bis(benzyloxy)-6-((benzyloxy)methyl)-3-oxotetrahydro-2H-pyran-2-yl)methyl)phosphonate；diethyl (((2 S,4S,5R,6R)-4,5-bis(benzyloxy)-6-((benzyloxy)methyl)-3-oxotetrahydro-2H-pyran-2-yl)methyl)phosphonate；(2S,4S,5R,6R)-2-(diethoxyphosphorylmethyl)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-3-one
• CAS: 172223-10-8
• 化学式: C₃₂H₃₉O₈P
• 分子量: 582.631
• InChiKey: OCNHEXJDEAEEOL-DHPILJFKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  41
• 可旋转键数：
  16
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  89.5
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  diethyl C-(3,4,6-tri-O-benzyl-α-D-arabino-hexosulopyranosyl)methanephosphonate 在 4-二甲氨基吡啶 、 盐酸羟胺 、 溶剂黄146 作用下， 以 四氢呋喃 、 吡啶 、 甲醇 为溶剂， 反应 2.0h， 生成 diethyl (((2S,4R,5S,6R)-3-(acetoxyimino)-4,5-bis(benzyloxy)-6-((benzyloxy)methyl)tetrahydro-2H-pyran-2-yl)methyl)phosphonate
  参考文献：
  名称：

  Stereoselective Synthesis of the Isosteric Phosphono Analogues of N-Acetyl-α-d-glucosamine 1-Phosphate and N-Acetyl-α-d-mannosamine 1-Phosphate

  摘要：

  The isosteric phosphono analogues of N-acetyl-alpha-D-glucosamine I-phosphate and N-acetyl-alpha-D-mannosamine l-phosphate (1 and 2) are stereoselectively synthesized starting from 2,3,5-tri-O-benzyl-D-arabinose (3b). Reaction of 3b with divinylzinc stereoselectively affords the glucoenitol 4c, the mercuriocyclization and subsequent iododemercuriation of which stereoselectively afford the alpha-C-glucopyranosyl iodide 6b with a free hydroxyl group at C-2. Temporary protection of the hydroxyl group and treatment with triethyl phosphite converts 6b into the corresponding phosphonate 7b. The free hydroxyl group of 7b is then converted into an acetamido group by oximation, acetylation of the oxime, reduction, and subsequent acetylation. The reduction of the oxime with diborane stereoselectively affords the gluco isomer, whereas catalytic hydrogenation gives the manno isomer. Acetylation and deprotection afford the desired products 1 and 2.

  DOI：

  10.1021/jo9519468
• 作为产物：
  描述：

  (2S,3R,4R,5R,6R)-4,5-bis(benzyloxy)-6-((benzyloxy)methyl)-2-(iodomethyl)tetrahydro-2H-pyran-3-ol 在 咪唑 、 水 、 乙酸酐 、 二甲基亚砜 、 三氟乙酸 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 5.0h， 生成 diethyl C-(3,4,6-tri-O-benzyl-α-D-arabino-hexosulopyranosyl)methanephosphonate
  参考文献：
  名称：

  Stereoselective Synthesis of the Isosteric Phosphono Analogues of N-Acetyl-α-d-glucosamine 1-Phosphate and N-Acetyl-α-d-mannosamine 1-Phosphate

  摘要：

  The isosteric phosphono analogues of N-acetyl-alpha-D-glucosamine I-phosphate and N-acetyl-alpha-D-mannosamine l-phosphate (1 and 2) are stereoselectively synthesized starting from 2,3,5-tri-O-benzyl-D-arabinose (3b). Reaction of 3b with divinylzinc stereoselectively affords the glucoenitol 4c, the mercuriocyclization and subsequent iododemercuriation of which stereoselectively afford the alpha-C-glucopyranosyl iodide 6b with a free hydroxyl group at C-2. Temporary protection of the hydroxyl group and treatment with triethyl phosphite converts 6b into the corresponding phosphonate 7b. The free hydroxyl group of 7b is then converted into an acetamido group by oximation, acetylation of the oxime, reduction, and subsequent acetylation. The reduction of the oxime with diborane stereoselectively affords the gluco isomer, whereas catalytic hydrogenation gives the manno isomer. Acetylation and deprotection afford the desired products 1 and 2.

  DOI：

  10.1021/jo9519468

文献信息

• First synthesis of the phosphono analogue of N-acetyl-α-<scp>D</scp>-mannosamine 1-phosphate
  作者：Laura Cipolla、Luigi Lay、Francesco Nicotra、Luigi Panza、Giovanni Russo

  DOI：10.1039/c39950001993

  日期：——

  treatment of the iodide with triethylphosphite to afford the corresponding phosphonate, deprotection of the hydroxy group, oxidation, oximation, catalytic hydrogenation and acetylation, afford the phosphono analogue of N-acetyl-α-D-mannosamine 1-phosphate.

  用二乙烯基锌对2,3,5-三-O-苄基-D-阿拉伯糖进行构图，随后进行巯基环化和碘脱汞立体选择性，得到α-C-吡喃葡萄糖基碘化物3，在C-2处具有游离羟基。暂时保护游离羟基，用亚磷酸三乙酯处理碘化物得到相应的膦酸酯，羟基去保护，氧化，肟化，催化氢化和乙酰化，得到N-乙酰基-α - D-甘露糖胺的膦酰基类似物1 -磷酸盐。
• Carbohydrate Phosphonate Derivatives as Modulators of Glycosylation
  申请人：AMGEN INC.

  公开号：US20150376221A1

  公开（公告）日：2015-12-31

  Compounds of Formula (I) are useful as modulators of glycosylation. Compounds of Formula (I) have the following structure: (I) and the definitions of the other variables are provided herein.

  化合物I的公式对糖基化的调节剂非常有用。化合物I的结构如下：(I)，其他变量的定义在此提供。
• Carbohydrate phosphonate derivatives as modulators of glycosylation
  申请人：AMGEN INC.

  公开号：US09328134B2

  公开（公告）日：2016-05-03

  Compounds of Formula (I) are useful as modulators of glycosylation. Compounds of Formula (I) have the following structure: (I) and the definitions of the other variables are provided herein.

  公式（I）的化合物可用作糖基化调节剂。公式（I）的化合物具有以下结构：（I），其他变量的定义在此提供。
• [EN] CARBOHYDRATE PHOSPHONATE DERIVATIVES AS MODULATORS OF GLYCOSYLATION<br/>[FR] DÉRIVÉS PHOSPHONATES DE GLUCIDES UTILISÉS COMME MODULATEURS DE LA GLYCOSYLATION
  申请人：AMGEN INC

  公开号：WO2014130613A3

  公开（公告）日：2014-11-06