but-3-en-1-yl 4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside | 195533-37-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: but-3-en-1-yl 4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside
• 英文别名: 3-buten-1-yl 4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside；[(2R,3S,6S)-3-acetyloxy-6-but-3-enoxy-3,6-dihydro-2H-pyran-2-yl]methyl acetate
• CAS: 195533-37-0
• 化学式: C₁₄H₂₀O₆
• 分子量: 284.309
• InChiKey: MJKWZTMDCMRTSI-MJBXVCDLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  20
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  but-3-en-1-yl 4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside 在 sodium methylate 作用下， 以 甲醇 为溶剂， 生成 but-3-enyl 2,3-dideoxy-α-D-erythro-hex-2-enopyranoside
  参考文献：
  名称：

  Palladium-Mediated Cyclization on Carbohydrate Templates. 2. Synthesis of Enantiopure Tricyclic Compounds

  摘要：

  The bromo substituted unsaturated carbohydrates 3a-f were prepared from 3,4,6-tri-O-acetyl-D-glucal by Ferrier reaction with the appropriate allylic or homoallylic alcohol, deacetylation followed by monosilylation with TBDMSCl, and then alkylation with BrCH2CBr=CH2. The N- and C-analogues 4a,b were synthesized by palladium alkylation of the intermediate carbonate with TsNHCH2CBr=CH2 and (MeO2C)(2)CHCH2CBr=CH2, respectively. Treatment of the unsaturated carbohydrates 3a, 4a, and 4b with a catalytic amount of Pd(OAc)(2)/PPh3 in CH3CN/H2O, in the presence of Bu4NHSO4 and NEt3, afforded the tricyclic compounds 5, 6, and 7, respectively. Under the same conditions, the analogue tricyclic compounds 8, 9, and 10 were formed starting from 3b-d. In the case of compounds 3e and 3f, the formation of the bicyclic glucal 11 via an already described beta-alkoxyelimination was only observed. Moreover, trapping of the sigma-alkylpalladium intermediate obtained from 3e with an external nucleophile yielded the 2-deoxy carbohydrate 12 and the 2,3-unsaturated sugar 13, using respectively sodium formate and sodium tetraphenylborate.

  DOI：

  10.1021/jo970817j
• 作为产物：
  描述：

  but-3-yn-1-yl 4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside 在 偶氮二异丁腈 、 三正丁基氢锡 、 水 、 silica gel 作用下， 以 甲苯 为溶剂， 反应 16.0h， 生成 but-3-en-1-yl 4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside
  参考文献：
  名称：

  Catalytic tin radical mediated tricyclisations. Part 1. Monocyclisation studies †

  摘要：

  提出了一种催化锡自由基介导的自由基级联反应的一般策略，其中在一步中构建了三个环。三环化过程的初始步骤是使用在1-O和/或4-O位具有不饱和取代基的2,3-脱氧-α-D-赤藓糖亨糖醛进行研究。用于1-O位取代基环化的底物是通过一种新型的氯化锌催化的Ferrier重排反应，将三-O-乙酰化的D-葡糖醛与不饱和醇反应而制备的，而用于4-O位取代基环化的底物则是通过烷基化或酰基化反应，对乙基6-O-保护的2,3-脱氧-α-D-赤藓糖亨糖醛进行处理。丙炔基取代基能有效环化，但丙烯基取代基则较差。丙炔酰基取代基在没有环化的情况下经历了氢锡化反应。

  DOI：

  10.1039/b000661k

文献信息

• Ceric(iv) ammonium nitrate-catalyzed glycosidation of glycals: a facile synthesis of 2,3-unsaturated glycosides
  作者：Jhillu S. Yadav、Basi V. Subba Reddy、Sushil Kumar Pandey

  DOI：10.1039/b009973m

  日期：——

  Glycosidation of glycals with alcohols in the presence of a catalytic amount of ceric(IV) ammonium nitrate under neutral conditions proceeds smoothly in refluxing acetonitrile to afford the corresponding 2,3-unsaturated glycosides in excellent yields.

  在温和条件下，以催化量的硝酸铈铵作为催化剂，糖酸内酯与醇在回流的乙腈中进行甘露糖基化反应，能够高效地生成相应的2,3-不饱和糖苷。
• Hafnium(IV) triflate as a highly efficient catalyst for Ferrier rearrangement of O- and S-nucleophiles with glycals
  作者：Yonghui Liu、Tianbang Song、Weijia Meng、Yun Xu、Peng George Wang、Wei Zhao

  DOI：10.1016/j.tetlet.2016.05.026

  日期：2016.6

  A highly efficient method to afford 2,3-unsaturated glycosides was described. In the presence of Hafnium(IV) triflate, a variety of 2,3-unsaturated-O- and S-glycosides have been obtained by stereoselective glycosylation of 3,4,6-tri-O-acetyl-d-glucal and hexa-O-acetyl-d-lactal with various acceptors in good isolated yields.

  描述了一种提供2，3-不饱和糖苷的高效方法。在铪（IV），三氟甲磺酸，各种2,3- unsaturated-存在ø -和š -glycosides已经通过的3,4,6-三-立体选择性糖基化得到ö乙酰基d -glucal和六ø乙酰基d -lactal在良好的分离产率的各种受体。
• Stereoselective synthesis of pseudoglycosides catalyzed by TeCl4 under mild conditions
  作者：Juliano C.R. Freitas、Túlio R. Couto、Antônio A.S. Paulino、João R. de Freitas Filho、Ivani Malvestiti、Roberta A. Oliveira、Paulo H. Menezes

  DOI：10.1016/j.tet.2012.09.073

  日期：2012.12

  Catalytic amounts of tellurium(IV) tetrachloride were used to promote the O-glycosylation of 3,4,6-tri-O-acetyl-D-glucal to give the corresponding 2,3-unsaturated-O-glycosides. With simple alcohols, the desired compounds were obtained in good yields and excellent anomeric selectivity in a short reaction time using only 2 mol % of the catalyst. The application of the method in the synthesis of a small set of glycopyranosides with rigid or flexible linkers gave the corresponding a anomers as products in good yields. Further applications of some of the synthesized compounds in allylation reaction of aldehydes gave the corresponding homoallylic alcohols in good yields. (C) 2012 Elsevier Ltd. All rights reserved.
• Exclusive Formation of a-Anomers in NbCl5-Promoted Ferrier Rearrangement for the Synthesis of 2,3-Unsaturated Glycosides
  作者：Rajendra M. Srivastava、Ronaldo N. de Oliveira、Adriana C. N. de Melo、Denis Sinou

  DOI：10.3987/com-06-10812

  日期：——