1,5-Anhydro-2-deoxy-3,4-O-isopropylidene-6-O-(tert-butyldimethylsilyl)-D-lyxo-hex-1-enitol | 161822-65-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: 1,5-Anhydro-2-deoxy-3,4-O-isopropylidene-6-O-(tert-butyldimethylsilyl)-D-lyxo-hex-1-enitol
• 英文别名: [(3aR,4R,7aR)-2,2-dimethyl-4,7a-dihydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl]methoxy-tert-butyl-dimethylsilane
• CAS: 161822-65-7
• 化学式: C₁₅H₂₈O₄Si
• 分子量: 300.47
• InChiKey: PMLRUXYWZMDFJO-JHJVBQTASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.44
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,5-Anhydro-2-deoxy-3,4-O-isopropylidene-6-O-(tert-butyldimethylsilyl)-D-lyxo-hex-1-enitol 在 叠氮基三甲基硅烷 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 48.5h， 生成 phenyl 2-azido-2-deoxy-3,4-O-isopropylidene-1-seleno-α-D-galactopyranoside
  参考文献：
  名称：

  从糖基中制备多种保护的 2-azido-2-deoxyglycopyranoses

  摘要：

  描述了从相应的糖类中制备出多种保护的 2-azido-2-deoxyglycopyranosides 的新的和有效的方法。糖基首先通过叠氮基-苯基硒基化作用转化为受保护的苯基 2-叠氮基-2-脱氧-硒基糖苷。根据存在的保护基团采用两种方法：在（二乙酰氧基碘）苯存在下制备全乙酰化糖醛（方法 A）或叠氮化三甲基甲硅烷和四正丁基氟化铵在 N-苯基硒代邻苯二甲酰亚胺用于过苄基化糖类（程序 B）。葡萄糖-甘露糖混合物 (90%) 从受保护的 d-glucal 中获得，而只有半乳糖异构体由受保护的 d-半乳醛 (75%) 形成。用 1,5-anhydro-2-deoxy-3,4-O-isopropylidene-d-lyxo-hex-l-enitol 和 1,5-anhydro-2-deoxy-3,4-O-isopropylidene-d-lyxo-hex-l-enitol 和其 6-0-乙酰基 I、6-0-烯丙基、6-0-苄基和

  DOI：

  10.1139/v95-046
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 、 2,6-anhydro-5-deoxy-3,4-O-isopropylidene-D-arabino-hex-5-enitol 在 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 48.0h， 以84%的产率得到1,5-Anhydro-2-deoxy-3,4-O-isopropylidene-6-O-(tert-butyldimethylsilyl)-D-lyxo-hex-1-enitol
  参考文献：
  名称：

  从糖基中制备多种保护的 2-azido-2-deoxyglycopyranoses

  摘要：

  描述了从相应的糖类中制备出多种保护的 2-azido-2-deoxyglycopyranosides 的新的和有效的方法。糖基首先通过叠氮基-苯基硒基化作用转化为受保护的苯基 2-叠氮基-2-脱氧-硒基糖苷。根据存在的保护基团采用两种方法：在（二乙酰氧基碘）苯存在下制备全乙酰化糖醛（方法 A）或叠氮化三甲基甲硅烷和四正丁基氟化铵在 N-苯基硒代邻苯二甲酰亚胺用于过苄基化糖类（程序 B）。葡萄糖-甘露糖混合物 (90%) 从受保护的 d-glucal 中获得，而只有半乳糖异构体由受保护的 d-半乳醛 (75%) 形成。用 1,5-anhydro-2-deoxy-3,4-O-isopropylidene-d-lyxo-hex-l-enitol 和 1,5-anhydro-2-deoxy-3,4-O-isopropylidene-d-lyxo-hex-l-enitol 和其 6-0-乙酰基 I、6-0-烯丙基、6-0-苄基和

  DOI：

  10.1139/v95-046

文献信息

• Trimethylsilylnitrate−Trimethylsilyl Azide:  A Novel Reagent System for the Synthesis of 2-Deoxyglycosyl Azides from Glycals. Application in the Synthesis of 2-Deoxy-β-<i>N</i>-glycopeptides
  作者：B. Gopal Reddy、K. P. Madhusudanan、Yashwant D. Vankar

  DOI：10.1021/jo0354948

  日期：2004.4.1

  1-azido 2-deoxy sugars in one step in fair to good yields. Galactals offer higher stereoselectivities than do the glucals. Reduction of the azide group with Ph3P−H2O to amino functionality followed by coupling with amino acids leads to the synthesis of novel 2-deoxy-β-N-glycopeptides irrespective of the geometry of initial azido sugars. Using this protocol, a new γ-sugar amino acid derivative is also procured

  包含Me 3 SiN 3和20mol％的Me 3 SiONO 2的新型试剂系统允许在一个步骤中将糖类转化为1-叠氮基2-脱氧糖，以公平至良好的产率。与葡萄糖相比，半乳糖具有更高的立体选择性。与初始叠氮糖的几何结构无关，用Ph 3 P-H 2 O将叠氮化物基团还原为氨基官能团，然后与氨基酸偶联可导致合成新型2-脱氧-β - N-糖肽。使用该协议，还可以购买新的γ-糖氨基酸衍生物。
• Cyclopropanation of glycals: Application to the synthesis of 2-deoxy-2-vinyl glycosides
  作者：Kenneth J. Henry、Bert Fraser-Reid

  DOI：10.1016/0040-4039(95)01926-9

  日期：1995.12

  have been found to undergo efficient Cyclopropanation with ethoxycarbonyl carbene with excellent facial selectivity, while di-O-acetyl-L-rhamnal exhibits lower facial selectivity. The cyclopropano glycals derived from glucal and galactal have been transformed into 2-deoxy-2-vinyl mannosides and galactosides, which are potentially valuable branched-chain sugars.

  已经发现适当保护的葡糖和半乳糖衍生物可以与乙氧基羰基卡宾一起进行有效的环丙烷化反应，并具有出色的面部选择性，而二-O-乙酰基-L-鼠李显示较低的面部选择性。衍生自葡萄糖和半乳糖的环丙糖已转化为2-脱氧-2-乙烯基甘露糖苷和半乳糖苷，它们是潜在有价值的支链糖。
• Seleno glycosides. 2. Synthesis of Phenyl 2-(N-Acetylamino)- and 2-Azido-2-deoxy-1-seleno-.alpha.-D-glycopyranosides via Azido-phenylselenylation of Diversely Protected Glycals
  作者：S. Czernecki、E. Ayadi、D. Randriamandimby

  DOI：10.1021/jo00105a051

  日期：1994.12

  Two methods are described for the preparation of diversely protected phenyl 2-azido-2-deoxy-alpha-D-selenoglycopyranosides from protected glycals. In the first one (method A), a peracetylated glycal is treated with sodium azide and diphenyl diselenide in the presence of (diacetoxyiodo)benzene in dichloromethane at rt. With 3,4,6-tri-O-acetyl-1,5-anhydro-2-deoxy-D-arabino-hex-1-enitol (tri-O-acetyl-D-glucal) an inseparable mixture of phenyl 2-azido-2-deoxy-alpha-gluco- and -alpha-manno-selenoglycosides is obtained (91% yield). With 3,4,6-tri-O-acetyl-1,5-anhydro-2-deoxy-D-lyxo-hex-1-enitol (tri-O-acetyl-D-galactal) only the alpha-galacto isomer is obtained (92%). Method A is not compatible with benzyl groups. In method B, a perbenzylated glycal is reacted with trimethylsilyl azide and tetra-n-butylammonium fluoride in the presence of N-phenylselenophthalimide. From protected D-glucal a gluco/manno mixture is obtained, whereas only the galacto isomer is formed from protected D-galactal (75% yield). The compatibility of method B with a variety of protecting groups is exemplified with 6-O-acetyl, 6-O-benzyl, and 6-O-(tert-butyldimethylsilyl)-3,4-O-isopropylidene-1,5-anhydro-2-deoxy-D-lyxo-hex-1-enitol. The same diastereocontrol is observed, and the alpha-D-galacto isomer is obtained (60-70% yield). Reduction of the azido group of these selenoglycosides with 1,3-propanedithiol in the presence of triethylamine and acetylation affords the corresponding phenyl 2-(N-acetylamino)-2-deoxy-alpha-D-selenoglycopyranosides in goed yield.