methyl 2,3-dideoxy-4,6-O-(phenylmethylene)-3-C-phenylsulfonyl-α-D-erythro-hex-2-enopyranoside | 273921-07-6

• 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-C-phenylsulfonyl-α-D-erythro-hex-2-enopyranoside
• 英文别名: methyl 2,3-dideoxy-4,6-O-phenylmethylene-3C-phenylsulfonyl-α-D-erythro-hex-2-enopyranoside；methyl 2,3-dideoxy-3-C-phenylsulfonyl-α-D-hex-2-enopyranoside；(2R,4aR,6S,8aR)-8-(benzenesulfonyl)-6-methoxy-2-phenyl-4,4a,6,8a-tetrahydropyrano[3,2-d][1,3]dioxine
• CAS: 273921-07-6
• 化学式: C₂₀H₂₀O₆S
• 分子量: 388.441
• InChiKey: RLSBWHIXXGLTOF-GSEOLPGOSA-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-C-phenylsulfonyl-α-D-erythro-hex-2-enopyranoside 在 palladium dihydroxide 吡啶 、 氢气 、 magnesium 作用下， 以 甲醇 、 乙醇 为溶剂， 反应 52.0h， 生成 methyl 2-(acetylamino)-2,3-dideoxy-4,6-O-(phenylmethylene)-α-D-ribo-hexopyranoside
  参考文献：
  名称：

  Vinylsulfone-modified carbohydrates: first general route to d-lividosamine (2-amino-2,3-dideoxy-d-glucose) and its new analogues

  摘要：

  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.

  DOI：

  10.1016/s0040-4020(00)01081-4
• 作为产物：
  描述：

  methyl 2,3-anhydro-4,6-O-benzilidene-α-D-mannopyranoside 在 magnesium monoperoxyphthalate hexahydrate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 四甲基胍 作用下， 以 吡啶 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 5.58h， 生成 methyl 2,3-dideoxy-4,6-O-(phenylmethylene)-3-C-phenylsulfonyl-α-D-erythro-hex-2-enopyranoside
  参考文献：
  名称：

  将胺非对映选择性地添加到乙烯基砜改性的碳水化合物中：一种高度灵活的合成新型脱氧氨基糖的方法

  摘要：

  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。

  DOI：

  10.1021/jo991380d

文献信息

• A Glycosylation Driven Strategy for the Synthesis of Anomerically Pure Vinyl Sulfone-modified Pent-2-enofuranoses and Hex-2-enopyranoses
  作者：Tanmaya Pathak、Aditya Kumar Sanki

  DOI：10.1055/s-2002-32960

  日期：——

  Both α- and β-anomers of vinyl sulfone-modified pent-2-enofuranosides have been synthesized for the first time by taking advantage of the formation of α- and β-methyl glycosides in almost equal ratio only from derivatives of D-xylose. The strategy was equally applicable in the synthesis of α- and β-anomers of vinyl sulfone-modified hex-2-enopyranosides where a D-glucose derivative was selected over

  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。
• Anomeric Configuration-Directed Diastereoselective C−C Bond Formation in Vinyl Sulfone-Modified Carbohydrates:  A General Route to Branched-Chain Sugars
  作者：Aditya K. Sanki、Cheravakkattu G. Suresh、Usha D. Falgune、Tanmaya Pathak

  DOI：10.1021/ol0342047

  日期：2003.4.1

  to vinyl sulfone-modified hex-2-enopyranosides and pent-2-enofuranosides. Nucleophiles add to the C-2 position from a direction opposite to that of the disposition of the anomeric methoxy group. This novel concept of anomeric configuration-directed stereocontrolled carbon-carbon bond formation in vinyl sulfone-modified carbohydrates is general in nature and has been implemented in the synthesis of

  [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。
• 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.
• 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。
• 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.