2,4,6-tri-O-acetyl-3-O-allyl-α-D-glucopyranosyl trichloroacetimidate | 147589-16-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,4,6-tri-O-acetyl-3-O-allyl-α-D-glucopyranosyl trichloroacetimidate
• 英文别名: 2,4,6-Tri-O-acetyl-3-O-allyl-alpha-D-glucopyranosyl trichloroacetimidate；[(2R,3R,4S,5R,6R)-3,5-diacetyloxy-4-prop-2-enoxy-6-(2,2,2-trichloroethanimidoyl)oxyoxan-2-yl]methyl acetate
• CAS: 147589-16-0
• 化学式: C₁₇H₂₂Cl₃NO₉
• 分子量: 490.722
• InChiKey: LJJVHBZFYPADPK-UXXRCYHCSA-N

物化性质

• 熔点：
  71-73 °C
• 沸点：
  481.9±55.0 °C(Predicted)
• 密度：
  1.46±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  30
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  130
• 氢给体数：
  1
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  2,4,6-tri-O-acetyl-3-O-allyl-α-D-glucopyranosyl trichloroacetimidate 在 三氟甲磺酸三甲基硅酯 、 palladium dichloride 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 3.0h， 生成 methyl 2-O-benzoyl-4,6-O-benzylidene-β-D-glucopyranosyl-(1->3)-2,4,6-tri-O-acetyl-β-D-glucopyranoside
  参考文献：
  名称：

  Synthesis of β-d-glucose oligosaccharides from Phytophthora parasitica

  摘要：

  The glucohexaose, beta-D-Glcp-(1 --> 3)-[beta-D-Glcp-(1 --> 3)-beta-D-Glcp-(1 --> 3)-(3-D-Glcp-(1 --> 6)]-(3-D-Glcp-(1 --> 3)-o-Glcp, was synthesized as its allyl glycoside via 3+3 strategy. The trisaccharide donor, 2,3,4,6-tetra-O-benzoyl-alpha-D-glucopyranosyl-(1 --> 3)-2,4,6-tri-O-acetyl-(3-D-glucopyranosyl-(1 --> 3)-2,4,6-tri-O-acetyl-alpha-D-glucopyranosyl trichloroacetimidate (11), was obtained by 3-selective coupling of isopropyl 4,6-O-benzylidene-1-thio-(3-D-glucopyranoside (2) with 2,3,4,6-tetra-O-benzoyl-(3-D-glucopyranosyl-(1 3)-2-O-acetyl-4,6-O-benzylidene-alpha-D-glucopyranosyl trichloroacetimidate (6), followed by hydrolysis, acetylation, dethiolation, and trichloroacetimidation. Meanwhile, the trisaccharide acceptor, allyl 2,3,4,6-tetra-O-benzoyl-(3-D-glucopyranosyl-(1 --> 3)-2-O-acetyl(3-D-glucopyranosyl-(1 3)-4,6-di-O-acetyl-2-O-benzoyl-alpha-D-glucopyranoside (14), was prepared by coupling of allyl 4,6-di-Oacetyl-2-O-benzoyl-alpha-D-glucopyranoside (12) with 6, followed by debenzylidenation. Condensation of 14 with 11, followed by deacylation, gave the target hexaoside. A (3-(1 ->3)-linked tetrasaccharide 29 was also synthesized with methyl 2-O-benzoyl-4,6-0benzylidene-(3-D-glucopyranosyl-(1-> 3)-2,4,6-tri-O-acetyl-(3-D-glucopyranoside (25) as the acceptor and acylated (3-(1 3)-linked disaccharide 21 as the donor. 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2003.08.004
• 作为产物：
  描述：

  (3R,4S)-3-[(4R)-2,2-二甲基-1,3-二氧戊环-4-基]-7,7-二甲基-4-丙-2-烯氧基-2,6,8-三氧杂双环[3.3.0]辛烷 在 吡啶 、 氨 、 potassium carbonate 、 溶剂黄146 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 33.0h， 生成 2,4,6-tri-O-acetyl-3-O-allyl-α-D-glucopyranosyl trichloroacetimidate
  参考文献：
  名称：

  Synthesis of β-(1→6)-branched β-(1→3) glucohexaose and its analogues containing an α-(1→3) linked bond with antitumor activity

  摘要：

  A beta-(1 --> 6)-branched beta-(1 --> 3)-glucohexaose, present in many biologically active polysaccharides from traditionally herbal medicines such as Ganoderma lucidum, Schizophyllum commune and Lentinus edodes, was synthesized as its lauryl glycoside 32, and its analogues 18, 20 and 33 containing an alpha-(l --> 3) linked bond were synthesized. It is interesting to find that coupling of a 3,6-branched acylated trisaccharide trichloroacetimidate donor 9 with 3,6-branched acceptors 13 and 16 with 3'-OH gave the alpha-(1 --> 3)linked hexasaccharides 17 and 19, respectively, in spite of the presence of C-2 ester capable of neighboring group participation. However, coupling of 9 with 4-methoxyphenyl 4,6-0-benzylidene-beta-D-glucopyranoside (27) selectively gave beta-(1 --> 3)-linked tetrasaccharide 28. Simple chemical transformation of the tetrasaccharide 28 gave acylated tetrasaccharide trichloroacetimidate 29. Coupling of 29 with lauryl (I --> 6)-linked disaccharide 26 with 3-OH gave beta-(I --> 3)-linked hexasaccharide 30 as the major product. Bioassay showed that in combination with the chemotherapeutic agent cyclophospamide (CPA), the hexaose 18 at a dose of 0.5-1 mg/kg substantially increased the inhibition of S 180 for CPA, but decreased the toxicity caused by CPA. Some of these oligosaccharides also inhibited U-14 noumenal tumor in mice effectively. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0968-0896(03)00118-4

文献信息

• Synthesis of a selectively protected trisaccharide building block that is part of xylose-containing carbohydrate chains from N-glycoproteins
  作者：János Kerékgyártó、Jos G.M. van der Ven、Johannis P. Kamerling、András Lipták、Johannes F.G. Vliegenthart

  DOI：10.1016/0008-6215(93)87009-h

  日期：1993.1

  The synthesis is reported of ethyl 4-O-[3-O-allyl-4,6-O-isopropylidene-2-O-(2,3,4-tri-O-acetyl-beta-D- xylopyranosyl)-beta-D-mannopyranosyl]-3,6-di-O-benzyl-2-deoxy-2-phthalim ido-1 - thio-beta-D-glucopyranoside (16), a key intermediate in the synthesis of xylose-containing carbohydrate chains from N-glycoproteins. Condensation of ethyl 3,6-di-O-benzyl-2-deoxy-2-phthalimido-1-thio-beta-D- glucopyranoside

  据报道合成了乙基4-O- [3-O-烯丙基-4,6-O-异亚丙基-2-O-（2,3,4-三-O-乙酰基-β-D-吡喃吡喃糖基）-β -D-甘露吡喃糖基] -3,6-二-O-苄基-2-脱氧-2-邻苯二甲酰亚胺基-1--硫代β-D-吡喃葡萄糖苷（16），是合成含木糖的碳水化合物链的关键中间体来自N-糖蛋白。乙基3,6-二-O-苄基-2-脱氧-2-邻苯二甲酰亚胺基-1-硫代-β-D-吡喃葡萄糖苷（5）与2,4,6-三-O-乙酰基-3-O-的缩合使用三氟甲磺酸银作为促进剂的烯丙基-α-D-吡喃葡萄糖基溴化物，得到β-连接的二糖衍生物8（84％）。8的O-脱乙酰基化，然后进行异亚丙基化，得到10，将其通过氧化还原转化为乙基4-O-（3-O-烯丙基-4,6-O-异亚丙基-β-D-甘露吡喃糖基）-3,6-二-O-苯甲酰基-2-脱氧-2-邻苯二甲酰亚胺-1-硫代-β-D-吡喃葡萄糖苷（12）。由三氟甲磺酸银促进的12与2
• Remote control of α- or β-stereoselectivity in (1→3)-glucosylations in the presence of a C-2 ester capable of neighboring-group participation
  作者：Ying Zeng、Jun Ning、Fanzuo Kong

  DOI：10.1016/s0008-6215(02)00455-x

  日期：2003.2

  beta-(1-->3)-linked acetylated disaccharide trichloroacetimidate as the donor and a glucoside with the 3-OH free as the acceptor, alpha-linked trisaccharides were obtained in spite of the C-2 neighboring group participation.

  在（1→3）葡萄糖基化反应中，原来存在于供体或受体中的糖基键可控制即将到来的键的立体选择性，即新形成的糖苷键具有与供体或受体相反的异头构型。受体。因此，使用具有非还原端的α-（1-> 3）-连接的二糖，其中3-OH游离为受体，乙酰化的葡萄糖基三氯乙酰亚氨酸酯为供体，或α-（1-> 3）-连接的乙酰化二糖三氯乙酰亚氨酸酯为供体，以3-羟基游离的葡萄糖苷为受体，得到β-连接的三糖。同时，对于具有非还原端的β-（1-> 3）连接的二糖，游离的3-OH为受体，乙酰化的葡萄糖基三氯乙酰亚氨酸酯为供体，或与β-（1->
• Pure α-linked products can be obtained in high yields in glycosylation with glucosyl trichloroacetimidate donors with a C2 ester capable of neighboring group participation
  作者：Ying Zeng、Jun Ning、Fanzuo Kong

  DOI：10.1016/s0040-4039(02)00584-1

  日期：2002.5

  Predominant or even pure (1-->3)-alpha-linked products can be generated in glycosylation with glucosyl trichloroacetimidate donors with a C2 ester capable of neighboring group participation. Benzoylation of either the donors or acceptors gave more beta-linkage, while 4,6-O-benzylidenation of the acceptor gave exclusive beta-glucosylation. 3-O-Glycosylation of the donor and the presence of a (1-->3)-beta-linkage in the oligosaccharide acceptor gave sole alpha-glucosylation. (C) 2002 Elsevier Science Ltd. All rights reserved.