2-丙烯-1-基 2-脱氧-4,6-O-(1-甲基乙亚基)-2-[(2,2,2-三氟乙酰基)氨基]-alpha-D-吡喃葡萄糖苷 | 139629-59-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 中文名称: 2-丙烯-1-基 2-脱氧-4,6-O-(1-甲基乙亚基)-2-[(2,2,2-三氟乙酰基)氨基]-alpha-D-吡喃葡萄糖苷
• 中文别名: 2-丙烯-1-基2-脱氧-4,6-O-(1-甲基乙亚基)-2-[(2,2,2-三氟乙酰基)氨基]-alpha-D-吡喃葡萄糖苷；烯丙基2-脱氧-4,6-O-亚异丙基-2-(三氟乙酰氨基)-Α-D-吡喃葡糖苷；1-O-烯丙基-2-脱氧-4,6-O-异亚丙基-2-(三氟乙酰氨基)-Α-D-吡喃葡萄糖苷；烯丙基 2-脱氧-4,6-O-亚异丙基-2-(三氟乙酰氨基)-Α-D-吡喃葡糖苷
• 英文名称: allyl 2-deoxy-4,6-O-isopropylidene-2-trifluoroacetamido-α-D-glucopyranoside
• 英文别名: Allyl 2-deoxy-4,6-O-isopropylidene-2-(trifluoroacetamido)-a-D-glucopyranoside；N-[(4aR,6S,7R,8R,8aS)-8-hydroxy-2,2-dimethyl-6-prop-2-enoxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-7-yl]-2,2,2-trifluoroacetamide
• CAS: 139629-59-7
• 化学式: C₁₄H₂₀F₃NO₆
• 分子量: 355.311
• InChiKey: IBHZTQBRCYUFOV-ILAIQSSSSA-N

物化性质

• 熔点：
  94-96 °C(lit.)
• 沸点：
  466.7±45.0 °C(Predicted)
• 密度：
  1.35±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  86.2
• 氢给体数：
  2
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  2-丙烯-1-基 2-脱氧-4,6-O-(1-甲基乙亚基)-2-[(2,2,2-三氟乙酰基)氨基]-alpha-D-吡喃葡萄糖苷 在 sodium hydroxide 、 sodium hydride 、 碳酸氢钠 作用下， 以 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 8.5h， 生成 allyl 2-deoxy-3-O-[(R)-3-(dodecyloxy)tetradecyl]-4,6-O-isopropylidene-2-[(2,2,2-trichloroethoxycarbonyl)amino]-α-D-glucopyranoside
  参考文献：
  名称：

  具有醚链的脂质A型吡喃羧酸的合成及其生物学活性。

  摘要：

  描述了在C-3'和C-4位置均具有醚链的脂质A型吡喃羧酸的合成及其对人U937细胞的生物活性。

  DOI：

  10.1016/s0008-6215(01)00134-3
• 作为产物：
  描述：

  D-氨基葡萄糖盐酸盐 在 盐酸 、 4-甲基苯磺酸吡啶 、 三乙胺 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 3.5h， 生成 2-丙烯-1-基 2-脱氧-4,6-O-(1-甲基乙亚基)-2-[(2,2,2-三氟乙酰基)氨基]-alpha-D-吡喃葡萄糖苷
  参考文献：
  名称：

  2-脱氧-2-[（（3R）-3-羟基十四烷酰胺基] -3-O-[（3R）-3-羟基四癸基]-α-D-吡喃葡萄糖基磷酸二氢盐和2-脱氧-2-[（3R）的合成-3-羟基十四烷酰胺基] -3-O-[（3R）-3-羟基十四烷基] -4-O-膦酰基-D-吡喃葡萄糖。

  摘要：

  Both a 3-O-alkyl lipid X analogue and its 4-O-phosphono isomer were synthesized from allyl 2-deoxy-4,6-O-isopropylidene-2-trifluoroacetamido-alpha-D-glucopyranoside.

  DOI：

  10.1016/0008-6215(91)89006-2

文献信息

• Synthesis of Carboxymethyl GLA-60 Ether Derivatives Containing an Olefin in Their Chains and Their LPS-Antagonistic Activities
  作者：Tsuyoshi Nakamura、Yukiko Watanabe、Masao Shiozaki、Saori Kanai、Shin-ichi Kurakata

  DOI：10.1246/bcsj.76.1011

  日期：2003.5

  Anomeric carboxymethyl GLA-60 olefine derivatives having ether chains instead of ester chains in their side chains were synthesized and their biological activities toward both human U937 cells and mouse PEC-macrophage cells were measured. The species-specific behavior of these compounds in humans (LPS-antagonistic) and mice (very weak LPS-antagonistic, but almost inactive) found this time was different from that in humans (LPS-antagonistic) and mice (endotoxic) found in the biosynthetic precursor of lipid A, such as lipid IVa. However, this fact also shows, interestingly enough, that a difference exists in the molecular recognition between human and mouse LPS receptors.

  合成了具有醚链而非酯链的异构体羧甲基GLA-60烯烃衍生物，并测定了它们对人类U937细胞和小鼠PEC-巨噬细胞的生物活性。这些化合物在人体（LPS拮抗作用）和小鼠（LPS拮抗作用非常弱，但几乎没有活性）中的物种特异性行为与脂质A的生物合成前体脂质IVa中发现的人类（LPS拮抗作用）和小鼠（内毒性）的行为不同。然而，这一事实有趣地表明，人类和小鼠LPS受体之间存在分子识别的差异。
• A Palladium-Catalyzed Glycosylation Reaction:  The de Novo Synthesis of Natural and Unnatural Glycosides
  作者：Ravula Satheesh Babu、George A. O'Doherty

  DOI：10.1021/ja037097k

  日期：2003.10.1

  sterospecific palladium-catalyzed glycosylation reaction of a variety of alcohols is reported. The reaction selectively converts alpha-2-substituted 6-carboxy-2H-pyran-3(6H)-ones into alpha-2-substituted 6-alkoxy-2H-pyran-3(6H)-ones with complete retention of configuration and similarly converts the pyranones with beta-carboxy groups into pyranones with beta-alkoxy groups. The reaction works equally

  报道了多种醇的高度立体选择性和立体特异性钯催化的糖基化反应。该反应选择性地将 α-2-取代的 6-羧基-2H-吡喃-3(6H)-酮转化为 α-2-取代的 6-烷氧基-2H-吡喃-3(6H)-酮，完全保留构型，类似地将带有 β-羧基的吡喃酮转化为带有 β-烷氧基的吡喃酮。该反应对基于氨基酸和基于碳水化合物的醇同样有效。为了证明该过程在碳水化合物化学中的效用，一些产品在另外两个步骤中被选择性地转化为 α-甘露糖苷。由于 2-取代的 6-羧基-2H-吡喃-3(6H)-酮是通过不对称合成制备的，因此该反应可用于制备 d- 或 l-吡喃酮。
• Synthesis of a 3-ether analogue of lipid A
  作者：Masao Shiozaki、Yoshiyuki Kobayashi、Masami Arai、Noboru Ishida、Tetsuo Hiraoka、Masahiro Nishijima、Sayuri Kuge、Toshiaki Otsuka、Yuzuru Akamatsu

  DOI：10.1016/0008-6215(91)89007-3

  日期：1991.12

  Lipid A 3-ether analogues were synthesized from allyl 2-deoxy-4,6-O-isopropylidene-2-trifluoroacetamido-alpha-D-glucopyr anoside and 3,4,6-tri-O-acetyl-2-trifluoroacetamido-alpha-D-glucopyranosyl bromide. The compound lost completely the endotoxic activity.

  由烯丙基2-脱氧-4,6-O-异亚丙基-2-三氟乙酰胺基-α-D-葡萄糖吡喃糖苷和3,4,6-三-O-乙酰基-2-三氟乙酰胺基-α合成脂质A 3-醚类似物-D-吡喃葡萄糖基溴化物。该化合物完全丧失了内毒活性。
• Synthesis of 2-Deoxy-2-((2S,3R)-(2-fluoro-3-hydroxytetradecanoly)amino)-3-O-((3R)-3-tetradecanoyloxytetradecanoyl)-D-glucopyranose 4-(Dihydrogen Phosphate) and 2-Deoxy-2-((2R,3S)-(2-fluoro-3-hydroxytetradecanoyl)amino)-3-O-((3R)-3-tetradecanoyloxytetradecanoyl)-D-glucopyranose 4-(Dihydrogen Phosphate).
  作者：Yoshiyuki KOBAYASHI、Noboru ISHIDA、Masami ARAI、Masao SHIOZAKI、Tetsuo HIRAOKA、Masahiro NISHIJIMA、Sayuri KUGE、Toshiaki OTSUKA、Yuzuru AKAMATSU

  DOI：10.1248/cpb.40.333

  日期：——

  2-Deoxy-2-[(2S, 3R)-(2-fluoro-3-hydroxytetradecanoyl)amino]3-O-[(3R)-3-tetradecanoyloxytetradecanoyl]-D-glucopyranose 4-(dihydrogen phosphate) and 2-deoxy-2-[(2R, 3S)-(2-fluoro-3-hydroxytetradecanoyl)amino]-3-O-[(3R)-3-tetradecanoyloxytetradecanoyl]-D-glucopyranose 4-(dihydrogen phosphate) were synthesized. The (2S, 3R)-compound (9a) was a little more active than GLA-60 in the prostaglandin D2 releasing test on macrophages, and the(2R, 3S)-compound (9b) was almost inactive.

  合成了2-脱氧-2-[(2S, 3R)-(2-氟-3-羟基十四酸酰基)氨基]-3-O-[(3R)-3-十四酸酰氧基十四酸酰基]-D-葡萄糖吡喃糖4-(二氢磷酸盐)和2-脱氧-2-[(2R, 3S)-(2-氟-3-羟基十四酸酰基)氨基]-3-O-[(3R)-3-十四酸酰氧基十四酸酰基]-D-葡萄糖吡喃糖4-(二氢磷酸盐)。在巨噬细胞的前列腺素D2释放测试中，(2S, 3R)-化合物(9a)的活性略高于GLA-60，而(2R, 3S)-化合物(9b)几乎没有活性。
• Lipid A analogs having immunoactivating and anti-tumor activity
  申请人：Sankyo Company, Limited

  公开号：US05792840A1

  公开（公告）日：1998-08-11

  Compounds of formula (I): ##STR1## in which: R.sup.1 is hydroxy, protected hydroxy, fluorine, or --OP(O)(OH).sub.2 ; R.sup.2 and R.sup.3 are independently optionally substituted C.sub.6 -C.sub.20 aliphatic acyl; R.sup.4 is hydroxy, protected hydroxy, or --OP(O)(OH).sub.2, where at least one of R.sup.1 and R.sup.4 is --OP(O)(OH).sub.2 ; and R.sup.5 is hydroxy, protected hydroxy, or fluorine; provided that, except where at least one of R.sup.1 and R.sup.5 is fluorine, then at least one of R.sup.2 and R.sup.3 is a substituted C.sub.6 -C.sub.20 aliphatic acyl having (i) at least one halogen substituent and (ii) at least one substituent selected from the group consisting of halogen, hydroxy and C.sub.6 -C.sub.20 aliphatic acyloxy or at least one of R.sup.2 and R.sup.3 is a substituted C.sub.6 -C.sub.20 aliphatic acyl which is substituted by at least one halogen-substituted C.sub.6 -C.sub.20 aliphatic carboxylic acyloxy; have Lipid A-like activity and may be used for the treatment, prophylaxis, diagnosis and support of an animal suffering a disease or disorder arising from a deficiency in the immune system or from a tumor. They may be prepared by phosphorylation of corresponding compounds lacking a phosphoryl group.

  式（I）的化合物：其中：R.sup.1是羟基，保护羟基，氟或--OP（O）（OH）.sub.2；R.sup.2和R.sup.3分别是可选取代的C.sub.6-C.sub.20脂肪族酰基；R.sup.4是羟基，保护羟基，或--OP（O）（OH）.sub.2，其中至少有一个R.sup.1和R.sup.4是--OP（O）（OH）.sub.2；R.sup.5是羟基，保护羟基，或氟；但是，除非R.sup.1和R.sup.5中至少有一个是氟，否则R.sup.2和R.sup.3中至少有一个是具有（i）至少一个卤素取代基和（ii）至少一个取代基的取代C.sub.6-C.sub.20脂肪族酰基，所述取代基选自卤素、羟基和C.sub.6-C.sub.20脂肪族酰氧基，或R.sup.2和R.sup.3中至少有一个是经取代的C.sub.6-C.sub.20脂肪族酰基，该取代基由至少一个卤素取代的C.sub.6-C.sub.20脂肪族羧酰氧基取代；具有类似脂多糖A的活性，可用于治疗、预防、诊断和支持患有免疫系统缺陷或肿瘤引起的疾病或紊乱的动物。它们可以通过对缺乏磷酰基的对应化合物进行磷酸化来制备。