methyl 2,3-dideoxy-4,6-O-(phenylmethylene)-3-(phenylsulfonyl)-β-D-erythro-hex-2-enopyranoside | 273921-08-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: methyl 2,3-dideoxy-4,6-O-(phenylmethylene)-3-(phenylsulfonyl)-β-D-erythro-hex-2-enopyranoside
• 英文别名: methyl 2,3-dideoxy-4,6-O-(phenylmethylene)-3-C-phenylsulfonyl-β-D-erythro-hex-2-enopyranoside；methyl 2,3-dideoxy-4,6-O-phenylmethylene-3C-phenylsulfonyl-β-D-erythro-hex-2-enopyranoside；methyl 2,3-dideoxy-3-C-phenylsulfonyl-β-D-hex-2-enopyranoside；(2R,4aR,6R,8aR)-8-(benzenesulfonyl)-6-methoxy-2-phenyl-4,4a,6,8a-tetrahydropyrano[3,2-d][1,3]dioxine
• CAS: 273921-08-7
• 化学式: C₂₀H₂₀O₆S
• 分子量: 388.441
• InChiKey: RLSBWHIXXGLTOF-VBSBHUPXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  27
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  79.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 2,3-dideoxy-4,6-O-(phenylmethylene)-3-(phenylsulfonyl)-β-D-erythro-hex-2-enopyranoside 在 吡啶 、 盐酸 、 sodium hydride 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 28.5h， 生成 2-((2R,3S,6S)-4-Benzenesulfonyl-6-methanesulfonyloxymethyl-2-methoxy-3,6-dihydro-2H-pyran-3-yl)-malonic acid dimethyl ester
  参考文献：
  名称：

  在乙烯基砜改性的碳水化合物中，由端基构型指导的非对映选择性CC键形成：通向支链糖的一般途径。

  摘要：

  [结构：见正文]这是关于将碳亲核试剂非对映选择性地添加到乙烯基砜改性的hex-2-enopyranosides和pent-2-enofuranosides中的第一个报道。亲核试剂从与异头甲氧基基团的布置相反的方向加至C-2位置。这种在乙烯基砜改性的碳水化合物中由端基构型指导的立体控制的碳-碳键形成的新概念本质上是一般性的，并且已在新的己基吡喃糖基和戊呋喃糖基支链糖和高密度官能化的碳水化合物的合成中实现。

  DOI：

  10.1021/ol0342047
• 作为产物：
  描述：

  3-deoxy-1,2:5,6-di-O-isopropylidene-3-C-phenylsulfonyl-α-D-glucofuranose 在 吡啶 、 对甲苯磺酸 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 乙酰氯 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 12.25h， 生成 methyl 2,3-dideoxy-4,6-O-(phenylmethylene)-3-(phenylsulfonyl)-β-D-erythro-hex-2-enopyranoside
  参考文献：
  名称：

  用于合成异头纯乙烯基砜修饰的 Pent-2-enofuranoses 和 Hex-2-enopyranoses 的糖基化驱动策略

  摘要：

  通过仅从 D-木糖衍生物中以几乎相等的比例形成 α- 和 β- 甲基糖苷，首次合成了乙烯基砜修饰的戊-2-烯呋喃糖苷的α-和β-端基异构体。该策略同样适用于乙烯基砜修饰的 hex-2-enopyranosides 的 α- 和 β-端基异构体的合成，其中选择 D-葡萄糖衍生物而不是 D-阿洛糖衍生物作为起始材料，因为前者几乎只生产所需的甲基吡喃糖苷。

  DOI：

  10.1055/s-2002-32960

文献信息

• Diastereoselective Addition of Amines to Vinyl Sulfone Modified Carbohydrates:  A Highly Flexible Methodology for the Synthesis of New Classes of Deoxyaminosugars
  作者：Bindu Ravindran、Kandasamy Sakthivel、Cheravakkattu. G. Suresh、Tanmaya Pathak

  DOI：10.1021/jo991380d

  日期：2000.5.1

  addition reaction with various amines to develop a new methodology for the synthesis of new classes of aminosugars. Compound 5 alpha reacted with primary amines to generate gluco- derivatives, but secondary amines produced both gluco- (major) and manno- (minor) isomers. Compound 5 beta, on the other hand, produced only gluco- isomers with both primary and secondary amines. The stereochemical course of addition

  甲基2,3-二脱氧-4,6-O-（苯基亚甲基）-3-C-苯磺酰基-α-D-赤-己基-2-烯吡喃糖苷（5α）和甲基2,3-二脱氧-4,6- O-（苯基亚甲基）-3-C-苯基磺酰基-β-D-赤型-己基-2-烯吡喃糖苷（5 beta）已与多种胺进行迈克尔加成反应，从而开发出一种用于合成新型氨基糖的新方法。化合物5α与伯胺反应生成葡萄糖衍生物，但仲胺同时生成葡萄糖（主要）和甘露（次要）异构体。另一方面，化合物5β仅产生具有伯胺和仲胺的葡糖异构体。将一些胺添加到5α和5β的立体化学过程与将胺添加到3-硝基吡喃糖中的立体化学过程显着不同。
• Structural studies on C-2 substitution in a new set of synthetic aminodideoxy sugars: the steric bulk at C-2 influences the puckering of the pyranose ring
  作者：Chiravakkattu G. Suresh、Bindu Ravindran、Tanmaya Pathak、Krishnamurthy Narasimha Rao、J. Shashidharaprasad、N.K. Lokanath

  DOI：10.1016/s0008-6215(02)00208-2

  日期：2002.9

  selected aminodideoxy sugars with different group substitutions at the C-2 position were carried out. Product formation and X-ray crystallographic determination of the products from C-2 substitution in both alpha and beta anomers were studied. The observed variation in pyranose ring conformations in product compounds is explained in terms of C-2 substitution.

  进行了选定的C-2位置具有不同基团取代的氨基二脱氧糖的合成和单晶X射线结构分析。研究了α和β端基异构体中C-2取代产物的产物形成和X射线晶体学测定。用C-2取代解释了产物化合物中吡喃糖环构象的观察到的变化。
• Vinylsulfone-modified carbohydrates: first general route to d-lividosamine (2-amino-2,3-dideoxy-d-glucose) and its new analogues
  作者：Bindu Ravindran、Sachin G Deshpande、Tanmaya Pathak

  DOI：10.1016/s0040-4020(00)01081-4

  日期：2001.2

  A general route to D-lividosamine and its new analogues has been devised for the first time. The essence of the present synthetic route lies in the diastereoselective introduction of N-monoalkylated and N-dialkylated amines to C-2 carbons of methyl 2,3-dideoxy-3-C-phenylsulfonyl-alpha -D-hex-2-enopyranoside and methyl 2,3-dideoxy-3-C-phenylsulfonyl-P-D-hex-2-enopyranoside in equatorial configurations. The 2-amino-2,3-didcoxysugrs thus generated, are desulfonated reductively at C-3 sites to produce a known intermediate for the synthesis of D-lividosamine and several new 2-N-alkylamino- acid 2-N,N-dialkylamino-2,3-dideoxy analogues. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Comparison of the two anomers of methyl 2-(<i>N</i>-benzylamino)-2,3-dideoxy-4,6-<i>O</i>-phenylmethylene-3-<i>C</i>-phenylsulfonyl-<scp>D</scp>-glucopyranoside
  作者：Cheravakkattu G. Suresh、Bindu Ravindran、K. Narasimha Rao、Tanmaya Pathak

  DOI：10.1107/s0108270100007344

  日期：2000.8.15

  The title compounds, the alpha and beta anomers of methyl 2-(N-benzylamino)-2,3-dideoxy-4,6-O-phenylmethylene-3-C- phenylsulfonyl-D-glucopyranoside, C27H29NO6S, belong to the class of deoxyamino-sugars prepared by the addition of amines at C2. The endocyclic bond lengths of the pyranose ring in the alpha anomer are shorter than the corresponding bonds in the alpha anomer. The pyranose ring is in the chair form in the former, while it is in the boat form in the latter. These observed differences could be attributed to the C2 substitution of a bulky group. The phenylsulfonyl and benzylamino groups are in equatorial positions in the alpha anomer, while the benzylamino group is axial in the beta anomer.