ethyl 6-O-(tert-butyldimethylsilyl)-4-O-methoxycarbonyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside | 187990-50-7

• 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)-4-O-methoxycarbonyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside
• 英文别名: ethyl 6-O-(tert-butyldimethylsilyl)-4-O-methoxycarbonyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranozide；[(2R,3S,6S)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-6-ethoxy-3,6-dihydro-2H-pyran-3-yl] methyl carbonate
• CAS: 187990-50-7
• 化学式: C₁₆H₃₀O₆Si
• 分子量: 346.496
• InChiKey: HMKZBMFEKXQADF-MJBXVCDLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.48
• 重原子数：
  23
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ethyl 6-O-(tert-butyldimethylsilyl)-4-O-methoxycarbonyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside 在 tris-(dibenzylideneacetone)dipalladium(0) 叠氮基三甲基硅烷 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 ethyl 4-azido-6-O-(tert-butyldimethylsilyl)-2,3,4-trideoxy-α-D-erythro-hex-2-enopyranoside
  参考文献：
  名称：

  Efficient Synthesis of Some Unsaturated [1,2,3]‐Triazole‐Linked Glycoconjugates

  摘要：

  Thermal 1,3-dipolar cycloaddition of ethyl 4-azido-2,3,4-trideoxy-alpha-D- erythro -hex-2-enopyranosides with diethyl acetylenedicarboxylate or copper-catalyzed reaction with various functionalized alkynes gave the corresponding 1-(ethyl 2,3,4-trideoxy-alpha-D- erythro -hex-2-enopyranosid-4-yl)-1 H -1,2,3-triazole derivatives in quite good yields. These unsaturated compounds could be transformed into 1-(ethyl 2,3-di-O-acetyl-4-deoxy-alpha-D-mannopyranosid-4-yl)-1 H -1,2,3-triazoles by a simple dihydroxylation reaction. Copper-catalyzed condensation of ethyl 6-O-acetyl-4-azido-2,3,4-trideoxy-alpha-D- erythro-hex-2-enopyranoside with 1,3,5-triethynylbenzene or 1,3,5-tris(prop-2-ynyloxy)benzene afforded the corresponding trivalent glycoconjugate clusters.

  DOI：

  10.1080/07328300600803484
• 作为产物：
  描述：

  乙基 2,3-二脱氧-D-己-2-烯基吡喃糖苷 在 吡啶 、 咪唑 、 4-二甲氨基吡啶 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 生成 ethyl 6-O-(tert-butyldimethylsilyl)-4-O-methoxycarbonyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside
  参考文献：
  名称：

  Stereocontrolled palladium(0)-catalyzed preparation of unsaturated azidosugars: an easy access to 2- and 4-aminoglycosides

  摘要：

  The palladium-catalyzed substitution of alkyl 4,6-di-O-acetyl-alpha-D-erythro-hex-2-eno-pyranosides using NaN3 as the nucleophile gave predominantly the corresponding alkyl 2-azido-2,3,4-trideoxy-alpha-D-threo-hex-2-enopyranosides in the presence of Pd(PPh3)(4). However, alkyl 6-O-acetyl-4-azido-2,3,4-trideoxy-alpha-D-erythro-hex-2-enopyranosi des were obtained as the major products using Pd(PPh3)4 as the catalyst in the presence of dppb as the added ligand. Conversely, alkyl 6-O-(tert-butyidimethylsilyl)-4-0-methoxycarbonyl-2,3-dideoxy-alpha-D-hex-2-enopyranosides gave exclusively alkyl 4-azido-6-O-(tert-butyldimethylsilyi)-2,3,4-trideoxy-alpha-D-erythro-hex-2-enopyranosides in the presence of Pd-2(dba)(3)/PPh3 as the catalyst and Me3SiN3 as the nucleophile. The bis-hydroxylation followed by hydrogenation of ethyl 4-azido-2,3,4-trideoxy-alpha-D-erythro-hex-2-enopyranoside afforded the corresponding 4-amino-alpha-D-mannopyranoside, when propyl 2-azido-2,3,4-trideoxy-alpha-D-threo-hex-3-enopyranoside gave the 2-amino-alpha-D-altropyranoside under the same conditions. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.06.041

文献信息

• Palladium-Catalyzed Alkynylation (Sonogashira Coupling) at C-5 of the Uracil Moiety in Modified Unsaturated Pyranosyl Nucleosides
  作者：Denis Sinou、Rajendra Srivastava、Francisco Mendonça、Janaína dos Anjos、Sebastiao de Melo

  DOI：10.1055/s-2007-965976

  日期：2007.6

  Various unsaturated 4-(5-substituted-uracil-1-yl)glycopyranosides were synthesized in good yields by a palladium-catalyzed cross-coupling reaction of ethyl 6- O-( TERT-butyldimethylsilyl)-2,3,4-trideoxy-4-[5-iodo-2,4-dioxo-3,4-dihydropyrimidin-1(2 H)-yl]-α- D- ERYTHRO-hex-2-enopyranoside with a range of acetylenic derivatives.

  以钯催化的 6-O-(叔丁基二甲基甲硅烷基)-2,3,4-三氧- 4-[5-iodo-2,4-dioxo-3,4-dihydropyrimidin-1(2 H)-yl]-α-D-ERYTHRO-hex-2-enopyranoside 与一系列炔属衍生物。
• Palladium(0)-Catalyzed Allylation of Heterocyclic Nucleophiles with Unsaturated Carbohydrates
  作者：Denis Sinou、Ronaldo de Oliveira、Francisco Mendonça Jr.、Sebastiao de Melo、Rajendra Srivastava

  DOI：10.1055/s-2006-951507

  日期：2006.11

  Palladium(0)-catalyzed reaction of heterocyclic ambident nucleophiles with the carbonate of ethyl 6-O-tert-butyldimethylsilyl-2,3-dideoxy-4-a-D-erythro -hex-2-enopyranoside afforded the corresponding 4-aminated 2,3-unsaturated glycosides in quite good yields.

  钯 (0) 催化杂环双亲核试剂与乙基 6-O-叔丁基二甲基甲硅烷基-2,3-dideoxy-4-aD-erythro-hex-2-enopyranoside 的碳酸酯反应得到相应的 4-胺化 2,3 -不饱和糖苷的产率非常好。
• Stereochemistry in palladium- and nickel-catalyzed addition of phenylmagnesium bromide to unsaturated carbohydrates
  作者：Christophe Moineau、Véronique Bolitt、Denis Sinou

  DOI：10.1016/s0022-328x(98)00679-2

  日期：1998.9

  Palladium complex PdCl2(dppf) and nickel complex NiCl2(dppe) catalyze cross-coupling of unsaturated aryloxy carbohydrates with phenylmagnesium bromide. The nickel catalyst leads to inversion of configuration at the anomeric center while only retention occurs in the case of the palladium catalyst. This quite unusal retention is probably due to the influence of the ring oxygen atom

  钯配合物PdCl 2（dppf）和镍配合物NiCl 2（dppe）催化不饱和芳氧基碳水化合物与苯基溴化镁的交叉偶联。镍催化剂导致在端基异构体中心的构型反转，而在钯催化剂的情况下仅发生保留。这种非常不常用的保留可能是由于环氧原子的影响
• 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.
• Efficient Synthesis of Some Unsaturated [1,2,3]‐Triazole‐Linked Glycoconjugates
  作者：Ronaldo N. de Oliveira、Denis Sinou、Rajendra M. Srivastava

  DOI：10.1080/07328300600803484

  日期：2006.7

  Thermal 1,3-dipolar cycloaddition of ethyl 4-azido-2,3,4-trideoxy-alpha-D- erythro -hex-2-enopyranosides with diethyl acetylenedicarboxylate or copper-catalyzed reaction with various functionalized alkynes gave the corresponding 1-(ethyl 2,3,4-trideoxy-alpha-D- erythro -hex-2-enopyranosid-4-yl)-1 H -1,2,3-triazole derivatives in quite good yields. These unsaturated compounds could be transformed into 1-(ethyl 2,3-di-O-acetyl-4-deoxy-alpha-D-mannopyranosid-4-yl)-1 H -1,2,3-triazoles by a simple dihydroxylation reaction. Copper-catalyzed condensation of ethyl 6-O-acetyl-4-azido-2,3,4-trideoxy-alpha-D- erythro-hex-2-enopyranoside with 1,3,5-triethynylbenzene or 1,3,5-tris(prop-2-ynyloxy)benzene afforded the corresponding trivalent glycoconjugate clusters.