ethyl 6-O-(tert-butyldimethylsilyl)-2,3-dideoxy-β-D-erythro-hex-2-enopyranoside | 187990-51-8

• 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 6-O-(tert-butyldimethylsilyl)-2,3-dideoxy-β-D-erythro-hex-2-enopyranoside
• 英文别名: (2R,3S,6R)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-6-ethoxy-3,6-dihydro-2H-pyran-3-ol
• CAS: 187990-51-8
• 化学式: C₁₄H₂₈O₄Si
• 分子量: 288.459
• InChiKey: JSOXSNXLZDWGKP-YNEHKIRRSA-N

物化性质

• 沸点：
  342.0±42.0 °C(Predicted)
• 密度：
  1.00±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.69
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl 6-O-(tert-butyldimethylsilyl)-2,3-dideoxy-β-D-erythro-hex-2-enopyranoside 在 四溴化碳 、 四丁基氟化铵 、 三苯基膦 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 3.0h， 生成 ethyl 2-bromo-2,3,4-trideoxy-β-D-erythro-hex-3-enopyranoside
  参考文献：
  名称：

  水介质中铟促进的 Barbier 型烯丙基化：获得 2-C- 和 4-C-支链糖的新途径

  摘要：

  在 2-bromo-4-enopyranoside (3) 和 4-bromo-2-enopyranosides（2β、6α 和 6β）的水性介质中，铟促进的 Barbier 型烯丙基化为不同的 2-C-支链糖提供了新途径（7 , 11, 13) 和 4-C-支链糖 (18)。此外，除了这些 C 支糖的合成和表征之外，还讨论了这些反应的机理方面。

  DOI：

  10.1002/1615-4169(200206)344:3/4<319::aid-adsc319>3.0.co;2-s
• 作为产物：
  描述：

  ethyl 4,6-di-O-acetyl-2,3-dideoxy-β-D-erythro-hex-2-enopyranoside 在 咪唑 、 sodium methylate 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 24.0h， 生成 ethyl 6-O-(tert-butyldimethylsilyl)-2,3-dideoxy-β-D-erythro-hex-2-enopyranoside
  参考文献：
  名称：

  Palladium-Mediated Cyclization on Carbohydrate Templates. 1. Synthesis of Enantiopure Bicyclic Compounds

  摘要：

  The bromo unsaturated carbohydrates 30 and 9 were prepared from ethyl 4,6-di-O-acetyl-2,3-dideoxy-D-erythro-hex-2-enopyranoside (1a) and (7) by deacetylation followed by monosilylation with TBDMSCl and then alkylation with BrCH2CBr=CH2. The three analogues 6 and 10 were obtained using the same methodology after inversion at C-4 via a Mitsunobu reaction. The N- and C-analogues 4b and 5 were prepared by palladium alkylation of the carbonate 2d with TsNHCH(2)CBr=CH2 and (CO(2)Me)(2)CHCH2CBr=CH2, respectively. Treatment of the unsaturated carbohydrates 3a and 9 with a catalytic amount of Pd(OAc)(2)/PPh(3) in CH3CN/H2O in the presence of Bu(4)NHSO(4) and NEt(3) afforded the bicyclic compound 14a. The N- and C-analogues 14b and 14c were obtained using the same conditions and starting, respectively, from 4b and 5. On the other hand, treatment of the three derivatives 6 and 10 under these conditions gave the furanic structure 15. In the case of compound 30, performing the reaction in the presence of sodium formate yielded the bicyclic 2-deoxy carbohydrate 17.

  DOI：

  10.1021/jo961881o

文献信息

• Indium-Promoted Barbier-Type Allylations in Aqueous Media: New Access to 2-C- and 4-C-Branched Sugars
  作者：André Lubineau、Yves Canac、Nicole Le??Goff

  DOI：10.1002/1615-4169(200206)344:3/4<319::aid-adsc319>3.0.co;2-s

  日期：2002.6

  Indium-promoted Barbier-type allylations in aqueous media of 2-bromo-4-enopyranoside (3) and 4-bromo-2-enopyranosides (2β, 6α and 6β) provide a new access to different 2-C-branched sugars (7, 11, 13) and 4-C-branched sugar (18). Moreover, apart from the synthesis and characterization of these C-branched sugars, mechanistic aspects of these reactions are discussed.

  在 2-bromo-4-enopyranoside (3) 和 4-bromo-2-enopyranosides（2β、6α 和 6β）的水性介质中，铟促进的 Barbier 型烯丙基化为不同的 2-C-支链糖提供了新途径（7 , 11, 13) 和 4-C-支链糖 (18)。此外，除了这些 C 支糖的合成和表征之外，还讨论了这些反应的机理方面。
• Palladium-Mediated Cyclization on Carbohydrate Templates. 1. Synthesis of Enantiopure Bicyclic Compounds
  作者：Jean-Flaubert Nguefack、Véronique Bolitt、Denis Sinou

  DOI：10.1021/jo961881o

  日期：1997.3.1

  The bromo unsaturated carbohydrates 30 and 9 were prepared from ethyl 4,6-di-O-acetyl-2,3-dideoxy-D-erythro-hex-2-enopyranoside (1a) and (7) by deacetylation followed by monosilylation with TBDMSCl and then alkylation with BrCH2CBr=CH2. The three analogues 6 and 10 were obtained using the same methodology after inversion at C-4 via a Mitsunobu reaction. The N- and C-analogues 4b and 5 were prepared by palladium alkylation of the carbonate 2d with TsNHCH(2)CBr=CH2 and (CO(2)Me)(2)CHCH2CBr=CH2, respectively. Treatment of the unsaturated carbohydrates 3a and 9 with a catalytic amount of Pd(OAc)(2)/PPh(3) in CH3CN/H2O in the presence of Bu(4)NHSO(4) and NEt(3) afforded the bicyclic compound 14a. The N- and C-analogues 14b and 14c were obtained using the same conditions and starting, respectively, from 4b and 5. On the other hand, treatment of the three derivatives 6 and 10 under these conditions gave the furanic structure 15. In the case of compound 30, performing the reaction in the presence of sodium formate yielded the bicyclic 2-deoxy carbohydrate 17.