allyl 4-O-benzoyl-α-L-rhamnopyranoside | 114284-07-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: allyl 4-O-benzoyl-α-L-rhamnopyranoside
• 英文别名: [(2S,3R,4S,5R,6R)-4,5-dihydroxy-2-methyl-6-prop-2-enoxyoxan-3-yl] benzoate
• CAS: 114284-07-0
• 化学式: C₁₆H₂₀O₆
• 分子量: 308.331
• InChiKey: FOSJZLFXINIONT-KLLIRPSPSA-N

物化性质

• 沸点：
  462.3±45.0 °C(predicted)
• 密度：
  1.26±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  85.2
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  allyl 4-O-benzoyl-α-L-rhamnopyranoside 在 吡啶 、 三氟甲磺酸三甲基硅酯 、 乙酰氯 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 4.0h， 生成 allyl 3-O-acetyl-2,4-di-O-benzoyl-α-L-rhamnopyranosyl-(1->3)-2,4-di-O-benzoyl-α-L-rhamnopyranoside
  参考文献：
  名称：

  合成由α-（1→2）-和α-（1→3）连接的鼠李糖聚糖主链和GlcNAc侧链组成的寡糖的一般方法

  摘要：

  已经开发了用于合成由具有GlcNAc侧链的（1→2）-和（1→3）-连接的鼠李糖寡糖组成的寡糖的一般方法。例如，在植物致病性细菌丁香假单胞菌pv的脂多糖的O多糖部分中的两个十糖的高效且收敛的合成。获得了ribicola NCPPB 1010。这两个十糖分别由O多糖重复单元I + II和II + I组成。烯丙基3- ø -乙酰基-4- ö苯甲酰基α-L-吡喃鼠李糖苷，烯丙基2- ø -苯甲酰基-3- ø -氯乙酰-α-L-吡喃鼠李糖苷，2,4-二- ö苯甲酰基-3- ø -氯乙酰-α-L-吡喃鼠李糖三氯乙酰亚胺酯，和3- ö -乙酰基-2,4-二- ö苯甲酰基α-L-吡喃鼠李糖三氯乙酰亚胺酯，这是由高度选择性3-O-获得酰化用作关键合成子，以得到所需的具有3 3-和3 7-游离羟基的α-（1→2）-和α-（1→3）连接的鼠李糖单糖受体。因此，合成了几种二糖，然后由它们合成了四糖和六糖。六糖供

  DOI：

  10.1016/s0040-4020(03)00075-9
• 作为产物：
  描述：

  allyl 2,3-O-isopropylidene-α-L-rhamnopyranoside 在 三氟乙酸 作用下， 生成 allyl 4-O-benzoyl-α-L-rhamnopyranoside
  参考文献：
  名称：

  化学合成含有麻风分枝杆菌三糖半抗原的人工抗原。

  摘要：

  三糖烯丙基O-（3,4-二-O-甲基-β-D-吡喃葡萄糖基）-（1 ---- 4）-O-（2,3-二-O-甲基-α-L-鼠李糖吡喃糖基）-（1 ---- 2）-3-O-甲基-α-L-鼠李糖吡喃糖苷是由部分甲基化的单糖衍生物合成的。由三氟化硼醚化物促进的1，4-二-O-乙酰基-2，3-二-O-甲基-α-L-鼠李吡喃糖与适当的醇的缩合立体选择性地进行，收率很高。与2,4-二-O-乙酰基-3,6-二-O-甲基-α-D-吡喃葡萄糖基溴的选择性脱乙酰基和糖基化反应生成三糖。比较了单糖，二糖和三糖的丙烯酰胺共聚物特异性结合麻风患者抗体的能力。

  DOI：

  10.1016/0008-6215(88)84072-2

文献信息

• Synthesis of allyl and benzyl 4-O-(3,6-di-O-methyl-β-d-glucopyranosyl)-2,3-di-O-methyl-α-l-rhamnopyranoside
  作者：Jose R. Mariño-Albernas、Vicente Verez-Bencomo、Leandro Gonzalez、Carlos S. Perez

  DOI：10.1016/0008-6215(87)80099-x

  日期：1987.8

  Abstract Condensation of 2,4-di- O -acetyl-3,6-di- O -methyl-α- d -glucopyranosyl bromide with either allyl or benzyl 2,4-di- O -methyl-α- l -rhamnopyranoside in the presence of mercuric cyanide, followed by O -deacetylation, gave the title oligosaccharides in excellent yields.

  摘要2,4-二-O-乙酰基-3,6-二-O-甲基-α-d-吡喃葡萄糖基溴化物与烯丙基或苄基的2,4-二-O-甲基-α-1-鼠李糖吡喃糖苷缩合。氰化汞的存在，然后进行O-脱乙酰基反应，可以极好的收率得到标题寡糖。
• Trichloroacetimidate as an Efficient Protective Group for Alcohols
  作者：Biao Yu、Hai Yu、Yongzheng Hui、Xiuwen Han

  DOI：10.1055/s-1999-2736

  日期：1999.6

  The trichloroacetimidate is disclosed to be a general and efficient protective group for alcohols, which can be deprotected under mild acidic, basic, or neutral conditions, and has orthogonal stability with the acetate and tert-butyldimethylsilyl (TBS) protections.

  三氯乙亚氨酸酯是一种通用且有效的醇保护基团，可在弱酸性、碱性或中性条件下脱保护，并与乙酸酯和叔丁基二甲基甲硅烷基 (TBS) 保护具有正交稳定性。
• Total Synthesis of Candicanoside A, a Rearranged Cholestane Disaccharide, and Its 4″-<i>O</i>-(<i>p</i>-Methoxybenzoate) Congener
  作者：Pingping Tang、Biao Yu

  DOI：10.1002/ejoc.200800879

  日期：2009.1

  Candicanoside A (1) and its 4″-O-(p-methoxybenzoate) derivative 2 are congeners of the novel 24(2322)abeo-cholestane glycosides that occur in the genus Ornithogalum indigenous to Southern Africa and have remarkable cytostatic activities. These two saponins have been synthesized starting from dehydroisoandrosterone, D-glucose, and L-rhamnose in 37 and 44 steps, respectively. The reaction protocols feature

  Candicanoside A (1) 及其 4"-O-(p-甲氧基苯甲酸酯) 衍生物 2 是新型 24(2322)abeo-胆甾烷糖苷的同源物，它们存在于南部非洲土生土长的 Ornihogalum 属中，具有显着的细胞抑制活性。从脱氢异雄酮、D-葡萄糖和 L-鼠李糖开始，这两种皂苷分别经过 37 步和 44 步合成。反应方案的特点是立体控制的逐步糖基化，以糖基亚氨酸酯作为供体。重排类固醇苷元的合成采用 20-烷氧基介导的有角 18-甲基官能化、Johnson-Claisen 重排用于 C-20 烷基化、C-22 醇醛缩合和光解偶联α,β-不饱和内酯为关键步骤。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
• Synthesis of a hexasaccharide fragment of group E streptococci polysaccharide and the tetrasaccharide repeating unit of E. coli O7:K98:H6
  作者：Youlin Zeng、Fanzuo Kong

  DOI：10.1016/j.carres.2004.03.027

  日期：2004.6

  Syntheses of a hexasaccharide, the dimer of the repeating unit of the group E streptococci polysaccharide, and a tetrasaccharide, the repeating unit of the E. coli 07:K98:H6, were achieved by constructing alternate alpha-L-(l --> 2)- and alpha-L-(1 --> 3)linked L-rhamnopyranose backbones and substituting with beta-linked D-glucopyranose side chains for the former, and a D-gluco-pyranosyluronate branch for the latter, respectively, at O-2 of the L-rhamnose ring. (C) 2004 Elsevier Ltd. All rights reserved.Syntheses of a hexasaccharide, the dimer of the repeating unit of the group E streptococci polysaccharide, and a tetrasaccharide, the repeating unit of the E. coli O7:K98:H6, were achieved by constructing alternate alpha-L-(1 --> 2)- and alpha-L-(1 --> 3)-linked L-rhamnopyranose backbones and substituting with P-linked D-glucopyranose side chains for the former, and a D-gluco-pyranosyluronate branch for the latter, respectively, at O-2 of the L-rhamnose ring. (C) 2004 Elsevier Ltd. All rights reserved.
• A highly efficient and convergent synthesis of a hexasaccharide, a dimer of the repeating unit of the antigen O2 polysaccharide of Stenotrophomonas maltophilia
  作者：Wei Wang、Fanzuo Kong

  DOI：10.1016/s0008-6215(99)00004-x

  日期：1999.1

  A highly efficient and convergent synthesis of a hexasaccharide, which is a dimer of the repeating unit of the antigen O2 polysaccharide of Stenotrophomonas maltophilia, was achieved via coupling of 2,3,4-tri-O-acetyl-alpha-L-xylopyranosyl bromide with the tetrasaccharide, allyl 4-O-3-O-[4-O-(3,4-di-O-benzoyl-alpha-L-rhamnopyranosyl)-2,3,6-tri-O-benzoyl-alpha-D-mannopyranosyl]-4-benzoyl-alpha-L-rhamnopranosyl}-2,3,6-tri-O-benzoyl-alpha-D-mannopyranoside (18) by the Koenigs-Knorr method followed by deacylation. Compound 18 was readily prepared from the coupling of the disaccharide trichloroacetimidate, 4-O-(2-O-acetyl-3,4-di-O-benzoyl-alpha-L-rhamnopyranosyl)-2,3,6-tri-O-benzoyl-alpha-D-mannopyranosyl trichloroacetimidate (8) with the disaccharide acceptor, allyl 4-O-(2-O-acetyl-4-O-benzoyl-alpha-L-rhamnopyranosyl)-2,3,6-tri-O-benzoyl-alpha-D-mannopyranoside (16), and both 8 and 16 were prepared via the trichloroacetimidate method from simple starting materials. The sole use of acyl protecting groups substantially simplified protection and deprotection, and the allyl group at the reducing end of allyl 4-O-2-O[2,3,4-tri-O-acetyl-beta-L-xylopyranosyl]-3-O-[4-O-(2-O-(2,3,4-tri-O-acetyl-beta-L-rhamnopyranosyl)-3,4-di-O-benzoyl-alpha-L-rhamnopyranosyl)-2,3,6-tri-O-benzoyl-alpha-D-mannopyranosyl]-4-O-benzoyl-alpha-L-rhamnopyranosyl} -2,3,6-tri-O-benzoyl-alpha-D-mannopyranoside 19 allowed further chemical transformation. (C) 1999 Elsevier Science Ltd. All rights reserved.