methyl 5-O-benzyl-2,3-dideoxy-3-C-(p)-tolylsulfonyl-α-D-erythro-pent-2-enofuranoside | 476645-49-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl 5-O-benzyl-2,3-dideoxy-3-C-(p)-tolylsulfonyl-α-D-erythro-pent-2-enofuranoside
• 英文别名: (2R,5S)-5-methoxy-3-(4-methylphenyl)sulfonyl-2-(phenylmethoxymethyl)-2,5-dihydrofuran
• CAS: 476645-49-5
• 化学式: C₂₀H₂₂O₅S
• 分子量: 374.458
• InChiKey: PILQEAGCFVQSPR-QUCCMNQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  26
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  70.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 5-O-benzyl-2,3-dideoxy-3-C-(p)-tolylsulfonyl-α-D-erythro-pent-2-enofuranoside 在 magnesium 、 nickel dibromide 作用下， 以 甲醇 为溶剂， 反应 6.0h， 生成 methyl 5-O-benzyl-2-cyclohexylamino-2,3-dideoxy-α-D-arabinofuranoside
  参考文献：
  名称：

  Desulfonylation with Mg−MeOH−NiBr₂:  An Expedient Reagent System for the Synthesis of 2-Amino-2,3-dideoxy Furanosides

  摘要：

  A catalytic amount of NiBr2 with Mg-MeOH increases the efficiency of reductive desulfonylation of the beta-sulfonylated aminosugars. The Mg-MeOH-NiBr2 system has been utilized in the synthesis of 2-amino-2,3-dideoxypentofuranosides and 2-amino-2,3-dideoxyhexofuranosides. The yield of the desulfonylation improved dramatically from 0% with the known reagents to 44-75% with Mg-MeOH-NiBr2.

  DOI：

  10.1021/ol053082a
• 作为产物：
  描述：

  Toluene-4-sulfonic acid (2R,3R,4R,5S)-2-benzyloxymethyl-4-hydroxy-5-methoxy-tetrahydro-furan-3-yl ester 在 吡啶 、 sodium methylate 、 magnesium monoperoxyphthalate hexahydrate 、 甲基磺酰氯 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 26.5h， 生成 methyl 5-O-benzyl-2,3-dideoxy-3-C-(p)-tolylsulfonyl-α-D-erythro-pent-2-enofuranoside
  参考文献：
  名称：

  合成纯正的乙烯基砜改性的戊-2-烯呋喃糖苷和己-2-烯吡喃糖苷：一组高反应性迈克尔受体，可用于基于碳水化合物的合成子

  摘要：

  乙烯基砜改性的戊-2-烯呋喃糖苷的苄基或三苯甲基保护的α-和β-端基异构体的合成已通过适当掩蔽的甲基α - lyxo呋喃糖基环氧化合物或甲基β-核糖呋喃糖基环氧化合物的开环而引发。或通过苄基保护的3- O-甲苯磺酰基木糖呋喃糖苷和3- O-甲磺酰基核糖呋喃糖苷中离去基团的亲核取代被p-硫代甲酚。在后一组原料的情况下，α-和β-甲基糖苷仅由d-木糖的衍生物以几乎相等的比例形成。对于乙烯基砜改性的hex-2-enopyranosides的α和β端基异构体的合成，选择d-葡萄糖衍生物而不是d-阿洛糖衍生物作为起始原料，因为前者几乎只能生产所需的甲基吡喃糖苷，而后者产生了混合物。通过顺序应用氧化，甲磺酰化和碱诱导的消除反应，将所有硫化物均转化为乙烯基砜改性的碳水化合物。

  DOI：

  10.1016/s0040-4020(03)01059-7

文献信息

• Diastereoselective addition of planar N-heterocycles to vinyl sulfone-modified carbohydrates: a new route to isonucleosides
  作者：Aditya K. Sanki、Rahul Bhattacharya、Ananta Kumar Atta、Cheravakkattu G. Suresh、Tanmaya Pathak

  DOI：10.1016/j.tet.2008.08.050

  日期：2008.11

  C-2 positions of vinyl sulfone-modified carbohydrates provide an efficient and general route for the carbon–N-heterocycle bond formation. Therefore, the addition pattern of planar heterocycles, such as imidazole, triazole, thymine, and adenine to 3-C-phenylsulfonyl-hex-2-enopyranosides (1α/1β) and 3-C-p-toluenesulfonyl-pent-2-enofuranosides (2α/2β) was studied for developing a general methodology for

  在乙烯基砜改性的碳水化合物的C-2位上的平面N杂环的Michael型加成反应为碳N杂环键的形成提供了一条有效而通用的途径。因此，平面杂环，如咪唑，三唑，胸腺嘧啶和腺嘌呤到3-的加入图案Ç -苯磺酰基-己-2- enopyranosides（1α / 1β）和3- Ç - p甲苯磺酰-戊-2- enofuranosides （2α / 2β）进行了研究开发的一般方法为新类的异核苷掺入具有碳-合成ñ-呋喃糖基和吡喃糖基糖的C-2位的杂环键。在很大程度上，起始乙烯基砜的异头构型在决定添加杂环的非对映选择性中起着至关重要的作用。然而，三苯甲基保护的3 - C-对甲苯磺酰基-己-2-烯吡喃糖苷（33α / 33β）被认为是用于合成新种类的胸腺嘧啶和腺嘌呤脱氧异核苷的脱磺酰基和脱保护基的更实用的原料。
• 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。
• Diversity-Oriented Synthesis of Enantiopure Furofurans from Carbohydrates: An Expedient Approach with Built-in Michael Acceptor, Masked Aldehyde and Leaving Group in a Single Sugar Derivative
  作者：Chinmoy Manna、Tanmaya Pathak

  DOI：10.1002/ejoc.201300603

  日期：2013.9

  A single sugar molecule containing three functional groups, namely a masked aldehyde, a Michael acceptor and a leaving group, reacts with a series of β-dicarbonyl compounds and related reagents to form up to three new bonds and up to three new stereocenters. The configuration of the sugar derivative controls the diastereoselectivity in the formation of all the new bonds without a requirement for any

  包含三个官能团（即掩蔽醛、迈克尔受体和离去基团）的单个糖分子与一系列 β-二羰基化合物和相关试剂反应，形成最多三个新键和最多三个新立体中心。糖衍生物的构型控制了所有新键形成的非对映选择性，而不需要任何外部试剂进行不对称诱导。这种基于“手性池”的多样性导向合成策略导致了一系列基于不同支架和附属物变异的呋喃的形成，以及迄今为止未知的双环 3,8-二氧杂双环 [4.2.1] 壬烷家族.
• 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。
• Unusual addition of amines to C-2 of vinyl sulfone-modified-β-d-pent-2-enofuranosyl carbohydrates: synthesis of a new class of β-anomeric 2-amino-2,3-dideoxy-d-threo-pentofuranosides
  作者：Indrajit Das、Cheravakkattu G. Suresh、Jean-Luc Décout、Tanmaya Pathak

  DOI：10.1016/j.carres.2008.03.022

  日期：2008.6

  When 3-C-sulfonyl-pent-2-enofuranosides and 3-C-sulfonyl-hex-2-enofuranosides were reacted with primary and secondary amines, only the beta-anomeric methoxy group of the pent-2-enofuranoside did not cause any hindrance to incoming nitrogen nucleophiles. This resulted in the 'unusual' addition of amines, in which the diastereoselectivity of the reaction was overwhelmingly in favor of amino sugars of the D-arabino configuration. Selected products were desulfonylated to obtain a new class of beta-anomeric 2-amino-2,3-dideoxy-D-threo-pentofuranosides. (C) 2008 Elsevier Ltd. All rights reserved.