tris(isopropyl)silyl 2-acetamido-2,3-dideoxy-3-C-(2',6'-anhydro-7'-deoxy-D-glycero-D-manno-heptitol-7'-C-yl)-β-D-talopyranoside | 288574-27-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: tris(isopropyl)silyl 2-acetamido-2,3-dideoxy-3-C-(2',6'-anhydro-7'-deoxy-D-glycero-D-manno-heptitol-7'-C-yl)-β-D-talopyranoside
• 英文别名: N-[(2S,3S,4R,5R,6R)-5-hydroxy-6-(hydroxymethyl)-4-[[(2R,3S,4R,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]methyl]-2-tri(propan-2-yl)silyloxyoxan-3-yl]acetamide
• CAS: 288574-27-6
• 化学式: C₂₄H₄₇NO₁₀Si
• 分子量: 537.723
• InChiKey: LOGFCRCEEXDRIK-GFXKSZTESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.39
• 重原子数：
  36
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.96
• 拓扑面积：
  178
• 氢给体数：
  7
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  乙酸酐 、 tris(isopropyl)silyl 2-acetamido-2,3-dideoxy-3-C-(2',6'-anhydro-7'-deoxy-D-glycero-D-manno-heptitol-7'-C-yl)-β-D-talopyranoside 在 吡啶 、 4-二甲氨基吡啶 作用下， 反应 12.0h， 以93%的产率得到tris(isopropyl)silyl 2-acetamido-4,6-di-O-acetyl-2,3-dideoxy-3-C-(1',3',4',5'-tetra-O-acetyl-2',6'-anhydro-7'-deoxy-D-glycero-D-manno-heptitol-7'-C-yl)-β-D-talopyranoside
  参考文献：
  名称：

  The C-Disaccharide α-C(1→3)-Mannopyranoside of N-Acetylgalactosamine Is an Inhibitor of Glycohydrolases and of Human α-1,3-Fucosyltransferase VI. Its Epimer α-(1→3)-Mannopyranoside of N-Acetyltalosamine Is Not

  摘要：

  The radical C-glycosidation of (-)-(1S,4R,5R,6R)-6-endo-chloro-3-methylidene-5-exo-(phenylseleno)-7-oxabicyclo[2.2.1]heptan-2-one ((-)-4) with 2,3,4,6-tetra-O-acetyl-alpha-D-mannopyranosyl bromide gave (+)-(1S,3R,4R,5R,6R)-6-endo-chloro-5-exo-(phenylseleno)-3-endo-(1',3',4',5'-tetra-O-acetyl-2',6'-anhydro-7'-deoxy-D-glycero-D-manno-heptitol-7'-C-yl)-7-oxabicyclo[2.2.1]hept-2-one ((+)-5) that was converted into (+)-(1R,2S,5R,6R)-5-acetamido-3-chloro-2-anhydro-6-(1R,2S,5R,6R)-5-acetamido-3-chloro-2-hydroxy-6-(1',3',4',5'-tetra-O-acetyl)-2',6'-anhydro-7'-deoxy-D- glycero-D-manno-heptitol-7'-C-yl)cyclohex-3-en-1-yl acetate ((+)-10) and into (+)-(1R,2S,5R,6S)-5-bromo-3-chloro-2-hydroxy-6-(1',3',4',5',-tetra-O-acetyl-2',6'-anhydro-7'-deoxy-D-glycero-D-manno-heptitol-7'-C-yl)cyclohex-3-en-1-yl acetate ((+)-19). Ozonolysis of (+)-10 and further transformations provided 2-acetamido-2,3-dideoxy-3-C-(2',6'-anhydro-7'-deoxy-D-glycero-D-manno- heptitol-7'-C-yl)-D-galactose (alpha-C(1-->3)-D-mannopyranoside of N-acetylgalactosamine (alpha-D-Manp-(1-->3)CH2-D-GalNAc): 1). Displacement of the bromide (+)-19 with NaN3 in DMF provided the corresponding azide ((-)-20) following a SN2 mechanism. Ozonolysis of (-)-20 and further transformations led to 2-acetamido-2,3-dideoxy-3-C-(2',6'-anhydro-7'-deoxy-D-glycerol-D-manno-heptitol-7'-C-yl)-D-talose (alpha-C(1-->3)-D-mannopyranoside of N-acetyl D-talosamine (alpha-D-Manp-(1-->3)CH2-D-TalNAc): 2). The neutral C-disaccharide 1 inhibits several glycosidases (e.g., beta-galactosidase from jack bean with K-i = 7.5 mu M, alpha-L-fucosidase from human placenta with K-i = 28 mu M, beta-glucosidase from Caldocellum saccharolyticum with K-i = 18 mu M) and human alpha-1,3-fucosyltransferase VI (Fuc-TVI) with K-i = 120 mu M whereas it 2-epimer 2 does not. Double reciprocal analysis showed that the inhibition of Fuc-TVI by 1 displays a mixed pattern with respect to both the donor sugar GDP-fucose and the acceptor LacNAc with K-i of 123 and 128 mu M, respectively.

  DOI：

  10.1021/jo991952u
• 作为产物：
  描述：

  2,3,4,6-四-O-乙酰基-1-溴-Alpha-D-甘露糖 在 platinum(IV) oxide 吡啶 、 2,6-二甲基吡啶 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 锂硼氢 、 sodium azide 、 偶氮二异丁腈 、 三苯基氢化锡 、 氢气 、 三溴化硼 、 碳酸氢钠 、 臭氧 、 间氯过氧苯甲酸 、 3-氯苯甲酸 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 乙酸乙酯 、 N,N-二甲基甲酰胺 、 苯 为溶剂， -78.0~60.0 ℃ 、101.33 kPa 条件下， 反应 14.58h， 生成 tris(isopropyl)silyl 2-acetamido-2,3-dideoxy-3-C-(2',6'-anhydro-7'-deoxy-D-glycero-D-manno-heptitol-7'-C-yl)-β-D-talopyranoside
  参考文献：
  名称：

  The C-Disaccharide α-C(1→3)-Mannopyranoside of N-Acetylgalactosamine Is an Inhibitor of Glycohydrolases and of Human α-1,3-Fucosyltransferase VI. Its Epimer α-(1→3)-Mannopyranoside of N-Acetyltalosamine Is Not

  摘要：

  The radical C-glycosidation of (-)-(1S,4R,5R,6R)-6-endo-chloro-3-methylidene-5-exo-(phenylseleno)-7-oxabicyclo[2.2.1]heptan-2-one ((-)-4) with 2,3,4,6-tetra-O-acetyl-alpha-D-mannopyranosyl bromide gave (+)-(1S,3R,4R,5R,6R)-6-endo-chloro-5-exo-(phenylseleno)-3-endo-(1',3',4',5'-tetra-O-acetyl-2',6'-anhydro-7'-deoxy-D-glycero-D-manno-heptitol-7'-C-yl)-7-oxabicyclo[2.2.1]hept-2-one ((+)-5) that was converted into (+)-(1R,2S,5R,6R)-5-acetamido-3-chloro-2-anhydro-6-(1R,2S,5R,6R)-5-acetamido-3-chloro-2-hydroxy-6-(1',3',4',5'-tetra-O-acetyl)-2',6'-anhydro-7'-deoxy-D- glycero-D-manno-heptitol-7'-C-yl)cyclohex-3-en-1-yl acetate ((+)-10) and into (+)-(1R,2S,5R,6S)-5-bromo-3-chloro-2-hydroxy-6-(1',3',4',5',-tetra-O-acetyl-2',6'-anhydro-7'-deoxy-D-glycero-D-manno-heptitol-7'-C-yl)cyclohex-3-en-1-yl acetate ((+)-19). Ozonolysis of (+)-10 and further transformations provided 2-acetamido-2,3-dideoxy-3-C-(2',6'-anhydro-7'-deoxy-D-glycero-D-manno- heptitol-7'-C-yl)-D-galactose (alpha-C(1-->3)-D-mannopyranoside of N-acetylgalactosamine (alpha-D-Manp-(1-->3)CH2-D-GalNAc): 1). Displacement of the bromide (+)-19 with NaN3 in DMF provided the corresponding azide ((-)-20) following a SN2 mechanism. Ozonolysis of (-)-20 and further transformations led to 2-acetamido-2,3-dideoxy-3-C-(2',6'-anhydro-7'-deoxy-D-glycerol-D-manno-heptitol-7'-C-yl)-D-talose (alpha-C(1-->3)-D-mannopyranoside of N-acetyl D-talosamine (alpha-D-Manp-(1-->3)CH2-D-TalNAc): 2). The neutral C-disaccharide 1 inhibits several glycosidases (e.g., beta-galactosidase from jack bean with K-i = 7.5 mu M, alpha-L-fucosidase from human placenta with K-i = 28 mu M, beta-glucosidase from Caldocellum saccharolyticum with K-i = 18 mu M) and human alpha-1,3-fucosyltransferase VI (Fuc-TVI) with K-i = 120 mu M whereas it 2-epimer 2 does not. Double reciprocal analysis showed that the inhibition of Fuc-TVI by 1 displays a mixed pattern with respect to both the donor sugar GDP-fucose and the acceptor LacNAc with K-i of 123 and 128 mu M, respectively.

  DOI：

  10.1021/jo991952u

文献信息

• The C-Disaccharide α-C(1→3)-Mannopyranoside of <i>N</i>-Acetylgalactosamine Is an Inhibitor of Glycohydrolases and of Human α-1,3-Fucosyltransferase VI. Its Epimer α-(1→3)-Mannopyranoside of <i>N</i>-Acetyltalosamine Is Not
  作者：Carla Pasquarello、Sylviane Picasso、Raynald Demange、Martine Malissard、Eric G. Berger、Pierre Vogel

  DOI：10.1021/jo991952u

  日期：2000.7.1

  The radical C-glycosidation of (-)-(1S,4R,5R,6R)-6-endo-chloro-3-methylidene-5-exo-(phenylseleno)-7-oxabicyclo[2.2.1]heptan-2-one ((-)-4) with 2,3,4,6-tetra-O-acetyl-alpha-D-mannopyranosyl bromide gave (+)-(1S,3R,4R,5R,6R)-6-endo-chloro-5-exo-(phenylseleno)-3-endo-(1',3',4',5'-tetra-O-acetyl-2',6'-anhydro-7'-deoxy-D-glycero-D-manno-heptitol-7'-C-yl)-7-oxabicyclo[2.2.1]hept-2-one ((+)-5) that was converted into (+)-(1R,2S,5R,6R)-5-acetamido-3-chloro-2-anhydro-6-(1R,2S,5R,6R)-5-acetamido-3-chloro-2-hydroxy-6-(1',3',4',5'-tetra-O-acetyl)-2',6'-anhydro-7'-deoxy-D- glycero-D-manno-heptitol-7'-C-yl)cyclohex-3-en-1-yl acetate ((+)-10) and into (+)-(1R,2S,5R,6S)-5-bromo-3-chloro-2-hydroxy-6-(1',3',4',5',-tetra-O-acetyl-2',6'-anhydro-7'-deoxy-D-glycero-D-manno-heptitol-7'-C-yl)cyclohex-3-en-1-yl acetate ((+)-19). Ozonolysis of (+)-10 and further transformations provided 2-acetamido-2,3-dideoxy-3-C-(2',6'-anhydro-7'-deoxy-D-glycero-D-manno- heptitol-7'-C-yl)-D-galactose (alpha-C(1-->3)-D-mannopyranoside of N-acetylgalactosamine (alpha-D-Manp-(1-->3)CH2-D-GalNAc): 1). Displacement of the bromide (+)-19 with NaN3 in DMF provided the corresponding azide ((-)-20) following a SN2 mechanism. Ozonolysis of (-)-20 and further transformations led to 2-acetamido-2,3-dideoxy-3-C-(2',6'-anhydro-7'-deoxy-D-glycerol-D-manno-heptitol-7'-C-yl)-D-talose (alpha-C(1-->3)-D-mannopyranoside of N-acetyl D-talosamine (alpha-D-Manp-(1-->3)CH2-D-TalNAc): 2). The neutral C-disaccharide 1 inhibits several glycosidases (e.g., beta-galactosidase from jack bean with K-i = 7.5 mu M, alpha-L-fucosidase from human placenta with K-i = 28 mu M, beta-glucosidase from Caldocellum saccharolyticum with K-i = 18 mu M) and human alpha-1,3-fucosyltransferase VI (Fuc-TVI) with K-i = 120 mu M whereas it 2-epimer 2 does not. Double reciprocal analysis showed that the inhibition of Fuc-TVI by 1 displays a mixed pattern with respect to both the donor sugar GDP-fucose and the acceptor LacNAc with K-i of 123 and 128 mu M, respectively.