(2R,3R,4R,5R,6S)-2-Hydroxymethyl-6-[2-((3aR,5R,5aS,8aS,8bR)-2,2,7,7-tetramethyl-tetrahydro-bis[1,3]dioxolo[4,5-b;4',5'-d]pyran-5-yl)-ethyl]-tetrahydro-pyran-3,4,5-triol | 183604-63-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,3R,4R,5R,6S)-2-Hydroxymethyl-6-[2-((3aR,5R,5aS,8aS,8bR)-2,2,7,7-tetramethyl-tetrahydro-bis[1,3]dioxolo[4,5-b;4',5'-d]pyran-5-yl)-ethyl]-tetrahydro-pyran-3,4,5-triol
• 英文别名: (2R,3R,4R,5R,6S)-2-(hydroxymethyl)-6-[2-[(1S,2R,6R,8R,9S)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-8-yl]ethyl]oxane-3,4,5-triol
• CAS: 183604-63-9
• 化学式: C₁₉H₃₂O₁₀
• 分子量: 420.457
• InChiKey: XMDXGXDFADEHMM-INJZOAQMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.8
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  136
• 氢给体数：
  4
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  (2R,3R,4R,5R,6S)-2-Hydroxymethyl-6-[2-((3aR,5R,5aS,8aS,8bR)-2,2,7,7-tetramethyl-tetrahydro-bis[1,3]dioxolo[4,5-b;4',5'-d]pyran-5-yl)-ethyl]-tetrahydro-pyran-3,4,5-triol 在 Amberlite IR-120 作用下， 以 水 为溶剂， 以85%的产率得到(3R,4S,5R,6R)-6-[2-((2S,3R,4R,5R,6R)-3,4,5-Trihydroxy-6-hydroxymethyl-tetrahydro-pyran-2-yl)-ethyl]-tetrahydro-pyran-2,3,4,5-tetraol
  参考文献：
  名称：

  由C-甲酰基糖苷合成C-二糖

  摘要：

  C-甲酰基2,3：5,6-二-O-异亚丙基-d-呋喃呋喃糖苷（1）与2,3,4,6-四-O-苄基-d-吡喃半乳糖苷（2）之间的偶联半乳糖6-磷烷3生成相应的烯烃，这些烯烃在氢解后分别以56％和72％的收率得到β（1→6'）连接的C-二糖6和8。

  DOI：

  10.1016/0040-4039(96)01667-x
• 作为产物：
  描述：

  (2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl)methanal 在 palladium dihydroxide 、 甲烷 正丁基锂 、 4 A molecular sieve 、 氢气 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 乙醇 、 乙酸乙酯 为溶剂， -30.0 ℃ 、303.98 kPa 条件下， 生成 (2R,3R,4R,5R,6S)-2-Hydroxymethyl-6-[2-((3aR,5R,5aS,8aS,8bR)-2,2,7,7-tetramethyl-tetrahydro-bis[1,3]dioxolo[4,5-b;4',5'-d]pyran-5-yl)-ethyl]-tetrahydro-pyran-3,4,5-triol
  参考文献：
  名称：

  由C-甲酰基糖苷合成C-二糖

  摘要：

  C-甲酰基2,3：5,6-二-O-异亚丙基-d-呋喃呋喃糖苷（1）与2,3,4,6-四-O-苄基-d-吡喃半乳糖苷（2）之间的偶联半乳糖6-磷烷3生成相应的烯烃，这些烯烃在氢解后分别以56％和72％的收率得到β（1→6'）连接的C-二糖6和8。

  DOI：

  10.1016/0040-4039(96)01667-x

文献信息

• Synthesis of (1→6)-C-oligogalactosides by iterative Wittig olefination
  作者：Alessandro Dondoni、Martin Kleban、Helene Zuurmond、Alberto Marra

  DOI：10.1016/s0040-4039(98)01739-0

  日期：1998.10

  Carbon-linked β-d-(1→6)-di-, tri- and tetragalactopyranosides have been synthesized by an iterative Wittig olefination employing a galactosylmethylene phosphorane as building block.

  碳连接的β-d-（1→6）-di-，三-和四-吡喃半乳糖苷已经通过使用半乳糖基亚甲基膦烷作为结构单元的迭代Wittig烯烃化反应合成。
• Linear Total Synthetic Routes to β-<scp>d</scp>-<i>C</i>-(1,6)-Linked Oligoglucoses and Oligogalactoses up to Pentaoses by Iterative Wittig Olefination Assembly
  作者：Alessandro Dondoni、Alberto Marra、Mamoru Mizuno、Pier Paolo Giovannini

  DOI：10.1021/jo011142u

  日期：2002.6.1

  be seriously hampered by the 1,2-elimination of BnOH under the basic reaction conditions of the Wittig olefination, giving rise to the formation of substantial amounts of enopyranose. On the other hand, the ylide route B proved to be more efficient since very good yields (70-93%) of the isolated Wittig products were obtained throughout four consecutive cycles. Individual olefins and polyolefins obtained

  遵循两个互补的途径A和B，用于通过亚甲基桥逐步迭代组装β-D-（1,6）-吡喃葡萄糖和吡喃半乳糖残基。在路线A中，结构单元由2,3,4-三-O-苄基-6-O-叔丁基二苯基甲硅烷基（O-TBDPS）β-连接的半乳​​糖基亚甲基磷烷组成，而在路线B中，结构单元由β-连接具有类似的正交保护羟基的甲酰基C-吡喃葡萄糖苷。在路线A中，每个循环由磷烷结构单元与在C-5碳原子上带有甲酰基的糖残基反应（偶联）和将O-TBDPS保护的伯醇转化为甲酰基组成（武装） 。因此，路线A定义为醛路线。另一方面，路线B中的每个循环都涉及糖醛结构单元与C-6处带有磷叶立德的底物的偶联，以及在准备步骤中引入磷基作为叶立德官能度的前体。因此，路线B被定义为伊利德路线。事实证明，在维蒂希烯化反应的基本反应条件下，BnOH的1,2-消除严重阻碍了方法A的效率，从而导致形成大量的烯吡喃糖。另一方面，叶立德途径B被证明是更有效的，因
• Synthesis of α- and β-<scp>d</scp>-(1→6)-<i>C</i>-Disaccharides by Wittig Olefination of Formyl <i>C</i>-Glycosides with Glycopyranose 6-Phosphoranes
  作者：Alessandro Dondoni、Helene M. Zuurmond、Alessia Boscarato

  DOI：10.1021/jo971177n

  日期：1997.11.1

  The synthesis of (1-->6)-C-disaccharides by Wittig condensation of formyl C-glycofuranosides and pyranosides with galacto-and glucopyranose B-phosphoranes is described herein. The method involves the coupling of the sugar aldehydes with the ylides and the reduction of the double bond of the resulting sugar alkenes, in most of the cases by catalytic hydrogenation. The reduction with nickel boride or diimide is employed in some special cases. O-Benzyl protective groups are removed by catalytic hydrogenation either in the course of the reduction of the double bond or in a subsequent step, while O-isopropylidene groups are cleaved by treatment with Amberlite IR-120. In this way, eight free beta-D-(1-->6)-C-disaccharides have been prepared in 26-61% overall yield starting from B-linked formyl C-glycosides. These include C-linked analogues of the biologically active disaccharides allolactose (Gal beta 1,6Glc), gentiobiose (Glc beta 1,6Glc), and N-acetylamino disaccharides (GalNHAc beta,6Gal and GalNHAc beta 1,6Glc). Moreover, the synthesis of two alpha-D-(1-->6)-C-disaccharides is described from formyl C-furanosides. The limiting condition of the synthesis of these stereoisomers is the configurational instability of the alpha-linked formyl C-glycosides under the basic conditions of the Wittig olefination.
• Synthesis of C-disaccharides from C-formyl glycosides
  作者：Alessandro Dondoni、Alessia Boscarato、Helene Zuurmond

  DOI：10.1016/0040-4039(96)01667-x

  日期：1996.10

  ranoside (1) and 2,3,4,6-tetra-O-benzyl-d-galactopyranoside (2) with the protected galactose 6-phosphorane 3 leads to the corresponding olefins which upon hydrogenolysis give β (1 →6′)-linked C-disaccharides 6 and 8 in 56 and 72% yield, respectively.

  C-甲酰基2,3：5,6-二-O-异亚丙基-d-呋喃呋喃糖苷（1）与2,3,4,6-四-O-苄基-d-吡喃半乳糖苷（2）之间的偶联半乳糖6-磷烷3生成相应的烯烃，这些烯烃在氢解后分别以56％和72％的收率得到β（1→6'）连接的C-二糖6和8。