ethyl 2,3-dideoxy-α-D-threo-hex-2-enopyranoside

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: ethyl 2,3-dideoxy-α-D-threo-hex-2-enopyranoside
• 英文别名: (2R,3R,6S)-6-ethoxy-2-(hydroxymethyl)-3,6-dihydro-2H-pyran-3-ol
• 化学式: C₈H₁₄O₄
• 分子量: 174.197
• InChiKey: BKOQEDWPMMCGPM-PRJMDXOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl 2,3-dideoxy-α-D-threo-hex-2-enopyranoside 以 吡啶 、 二甲基亚砜 为溶剂， 反应 49.5h， 生成 ethyl 2,3,4-trideoxy-4-N-methylamino-6-O-p-toluenesulfonyl-α-D-erythro-hex-2-enopyranoside
  参考文献：
  名称：

  Stereocontrolled routes to cis-hydroxyamino sugars. Part VII. A synthesis of holacosamine

  摘要：

  甲基4,6-二-O-p-甲苯磺酰基-α-D-左-己-2-烯基吡喃苷4b在室温下与甲胺反应，只置换烯丙基磺酸酯，所得的4-N-甲基氨基糖的乙基脲醚与碘离子环化形成2-碘-噁唑烷酮13。该物质经过在丙酮中与碘化钠处理后，得到2,6-二碘代14a。去碘化后，经碱水解得到顺式-羟胺前体，经N-乙酰化和O-甲基化后得到已知的holacosaminide 1b。

  DOI：

  10.1139/v84-262
• 作为产物：
  描述：

  ethyl 4,6-di-O-benzoyl-2,3-dideoxy-α-D-threo-hex-2-enopyranoside 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 2.0h， 以75%的产率得到ethyl 2,3-dideoxy-α-D-threo-hex-2-enopyranoside
  参考文献：
  名称：

  Stereocontrolled routes to cis-hydroxyamino sugars. Part VII. A synthesis of holacosamine

  摘要：

  甲基4,6-二-O-p-甲苯磺酰基-α-D-左-己-2-烯基吡喃苷4b在室温下与甲胺反应，只置换烯丙基磺酸酯，所得的4-N-甲基氨基糖的乙基脲醚与碘离子环化形成2-碘-噁唑烷酮13。该物质经过在丙酮中与碘化钠处理后，得到2,6-二碘代14a。去碘化后，经碱水解得到顺式-羟胺前体，经N-乙酰化和O-甲基化后得到已知的holacosaminide 1b。

  DOI：

  10.1139/v84-262

文献信息

• Amine-linked diglycosides: Synthesis facilitated by the enhanced reactivity of allylic electrophiles, and glycosidase inhibition assays
  作者：Ian Cumpstey、Jens Frigell、Elias Pershagen、Tashfeen Akhtar、Elena Moreno-Clavijo、Inmaculada Robina、Dominic S Alonzi、Terry D Butters

  DOI：10.3762/bjoc.7.128

  日期：——

  Diglycose derivatives, consisting of two monosaccharides linked at non-anomeric positions by a bridging nitrogen atom, have been synthesised. Conversion of one of the precursor monosaccharide coupling components into an unsaturated derivative enhances its electrophilicity at the allylic position, facilitating coupling reactions. Mitsunobu coupling between nosylamides and 2,3-unsaturated-4-alcohols gave the 4-amino-pseudodisaccharides with inversion of configuration as single regio- and diastereoisomers. A palladium-catalysed coupling between an amine and a 2,3-unsaturated 4-trichloroacetimidate gave a 2-amino-pseudodisaccharide as the major product, along with other minor products. Derivatisation of the C=C double bond in pseudodisaccharides allowed the formation of Man(N4–6)Glc and Man(N4–6)Man diglycosides. The amine-linked diglycosides were found to show weak glycosidase inhibitory activity.

  由两个单糖通过桥接氮原子在非异头位置连接而成的双糖衍生物已经合成出来。将其中一个前体单糖耦合组分转化为不饱和衍生物，增强了其在烯丙基位置的亲电性，从而促进了耦合反应。nosyl酰胺和2,3-不饱和-4-醇之间的Mitsunobu耦合得到了反转构型的4-氨基-假双糖，作为单一的区位和对映异构体。胺和2,3-不饱和的4-三氯乙酰亚胺之间的钯催化耦合得到了2-氨基-假双糖作为主要产物，同时还得到了其他次要产物。在假双糖中对C=C双键的衍生化允许形成Man(N4–6)Glc和Man(N4–6)Man双糖苷。发现胺连接的双糖苷显示出较弱的糖苷酶抑制活性。
• Efficient Pseudo-enantiomeric Carbohydrate Olefin Ligands
  作者：Holger Grugel、Fabian Albrecht、Tobias Minuth、Mike M. K. Boysen

  DOI：10.1021/ol3015896

  日期：2012.7.20

  pseudo-enantiomeric olefin ligands were designed from d-glucose and d-galactose. These ligands yield consistently excellent levels of enantioselectivity in Rh(I)-catalyzed 1,4-additions of aryl- and alkenylboronic acids to achiral enones and high diastereoselectivity with chiral substrates. Contrary to established olefin ligands, they are obtained enantiomerically pure via short syntheses without racemic

  由d-葡萄糖和d-半乳糖设计了高效的假对映体烯烃配体。这些配体在Rh（I）催化的芳基和烯基硼酸向非手性烯酮的1,4-加成反应中始终产生优异的对映选择性，并具有手性底物的高非对映选择性。与已建立的烯烃配体相反，它们是通过短合成法得到对映体纯的，没有外消旋拆分步骤，这使它们成为具有烯烃供体位点的手性配体的重要补充。
• Cis - oxyamination routes to amimo sugars: A simple synthesis of holacosamine
  作者：Michael Georges、Bert Fraser-Reid

  DOI：10.1016/s0040-4039(01)83000-8

  日期：1981.1

  The known D-threo hex-2-enopyranoside 1a is converted into an N-methyl allyl amine, the methyl urethane of which undergoes electrophile-induced cyclisation to give the iodocyclic urethane 9. The cis relationship of H3 and H4 in the latter is confirmed by NMR spectroscopy. Reduction at C2 and C6 is done simultaneously and the cyclic urethane is hydrolysed. The amino group is then acetylated and the

  将已知的D-苏式hex-2-enopyranoside 1a转化为N-甲基烯丙基胺，对其甲基氨基甲酸酯进行亲电诱导的环化反应，得到碘代氨基甲酸乙酯9。证实了后者中H3和H4的顺式关系通过NMR光谱。同时在C2和C6处还原，然后将环状氨基甲酸酯水解。然后氨基被乙酰化而羟基被甲基化。
• Baer, Hans H.; Hanna, Zaher S., Canadian Journal of Chemistry, 1981, vol. 59, p. 889 - 906
  作者：Baer, Hans H.、Hanna, Zaher S.

  DOI：——

  日期：——
• NEIRABEYEH, MAMDOUH AL.;ROLLIN, PATRICK, J. CARBOHYDR. CHEM., 9,(1990) N, C. 471-478
  作者：NEIRABEYEH, MAMDOUH AL.、ROLLIN, PATRICK

  DOI：——

  日期：——