(R)-2-azido-1-hexadecanol | 402923-06-2

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 英文名称: (R)-2-azido-1-hexadecanol
• 英文别名: (2R)-2-azidohexadecan-1-ol
• CAS: 402923-06-2
• 化学式: C₁₆H₃₃N₃O
• 分子量: 283.458
• InChiKey: PKAVSQCGBHDYKU-MRXNPFEDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.7
• 重原子数：
  20
• 可旋转键数：
  15
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  34.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (R)-2-azido-1-hexadecanol 在 三氟甲磺酸三甲基硅酯 、 sodium methylate 、 三苯基膦 作用下， 以 甲醇 、 二氯甲烷 、 苯 为溶剂， 反应 40.0h， 生成 (2R)-2-hexadecanoylaminohexadecyl β-D-galactopyranoside
  参考文献：
  名称：

  Syntheses and interfacial behaviour of neoglycolipid analogues of glycosyl ceramides

  摘要：

  Four glycosyl ceramides analogues having D-galactose or 2-acetamido-2-deoxy-D-glucose moieties linked to enantiomeric lipids have been synthesised to study their interfacial behaviour at the air \ water interface. The lipid chains were prepared in two steps by opening 1,2-epoxyhexadecane using Jacobsen kinetic hydrolytic resolution (KHR) followed by an azidosilylation reaction of the diol so obtained. Glycosylation reactions were realised either with 2,3,4,6-tetra-O-benzoyl-alpha -D-galactopyranosyl trichloroacetimidate or 1,3,4,6-tetra-O-acetyl-2-allyloxycarbonylamino-2-deoxy-beta -D-glucopyranose as donors and (2R)- or (2S)-2-azidohexadecanol derivatives as acceptors. Transformation of the azido glycosides into N-acylated products was done by a modified Staudinger reaction in the presence of fatty acyl chlorides. The four neoglycolipids are able to form a condensed monolayer at the air \ water interface; their pi -A isotherm diagrams are similar to that described for the natural glycosyl ceramides. The detailed analysis of the isotherms, taking into account the chirality of the lipid chains, allowed to determine the contribution of the different parts of the molecule under the monolayer packing. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(01)00255-5
• 作为产物：
  描述：

  1,2-十六烷二醇 在 叠氮基三甲基硅烷 、 偶氮二甲酸二异丙酯 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 生成 (R)-2-azido-1-hexadecanol
  参考文献：
  名称：

  Regioselective and Stereospecific Azidation of 1,2- and 1,3-Diols by Azidotrimethylsilane via a Mitsunobu Reaction

  摘要：

  A one-pot regio- and stereospecific azidation reaction of 1,2- and 1,3-diols with azidotrimethylsilane (Me3SiN3) via a Mitsunobu reaction has been achieved. With 1,2- and 1,3-diols, the reaction of triphenylphosphine, diisopropyl azodicarboxylate, and Me3SiN3 in dichloromethane gave regioselective azidation at C-2 and C-3, respectively, in good yield (74-90% combined yield of 1a + 1b or of 2a + 2b). However, application of the same reaction conditions to a 1,4-diol led to the exclusive formation of the cyclic ether. The regioselectivity of this one-pot reaction is influenced by the solvent, the degree of steric bulk at C-2 of the 1,2-diol or at C-3 of the 1,3-diol, and the presence of electron-donating and electron-withdrawing groups near the secondary carbinol carbon. This selectivity is discussed in terms of the mechanistic model proposed by Mathieu-Pelta and Evans (Mathieu-Pelta, I.; Evans, S. A., Jr. J. Org. Chem. 1898, 57, 3409-3413), which involves reaction of the dioxaphospholane intermediate with Me3SiN3 to form oxyphosphonium ions 4 and 5.

  DOI：

  10.1021/jo9906375

文献信息

• Regioselective and Stereospecific Azidation of 1,2- and 1,3-Diols by Azidotrimethylsilane via a Mitsunobu Reaction
  作者：Linli He、Meni Wanunu、Hoe-Sup Byun、Robert Bittman

  DOI：10.1021/jo9906375

  日期：1999.8.1

  A one-pot regio- and stereospecific azidation reaction of 1,2- and 1,3-diols with azidotrimethylsilane (Me3SiN3) via a Mitsunobu reaction has been achieved. With 1,2- and 1,3-diols, the reaction of triphenylphosphine, diisopropyl azodicarboxylate, and Me3SiN3 in dichloromethane gave regioselective azidation at C-2 and C-3, respectively, in good yield (74-90% combined yield of 1a + 1b or of 2a + 2b). However, application of the same reaction conditions to a 1,4-diol led to the exclusive formation of the cyclic ether. The regioselectivity of this one-pot reaction is influenced by the solvent, the degree of steric bulk at C-2 of the 1,2-diol or at C-3 of the 1,3-diol, and the presence of electron-donating and electron-withdrawing groups near the secondary carbinol carbon. This selectivity is discussed in terms of the mechanistic model proposed by Mathieu-Pelta and Evans (Mathieu-Pelta, I.; Evans, S. A., Jr. J. Org. Chem. 1898, 57, 3409-3413), which involves reaction of the dioxaphospholane intermediate with Me3SiN3 to form oxyphosphonium ions 4 and 5.
• Syntheses and interfacial behaviour of neoglycolipid analogues of glycosyl ceramides
  作者：Dominique Lafont、Marie-Noëlle Bouchu、Agnès Girard-Egrot、Paul Boullanger

  DOI：10.1016/s0008-6215(01)00255-5

  日期：2001.11

  Four glycosyl ceramides analogues having D-galactose or 2-acetamido-2-deoxy-D-glucose moieties linked to enantiomeric lipids have been synthesised to study their interfacial behaviour at the air \ water interface. The lipid chains were prepared in two steps by opening 1,2-epoxyhexadecane using Jacobsen kinetic hydrolytic resolution (KHR) followed by an azidosilylation reaction of the diol so obtained. Glycosylation reactions were realised either with 2,3,4,6-tetra-O-benzoyl-alpha -D-galactopyranosyl trichloroacetimidate or 1,3,4,6-tetra-O-acetyl-2-allyloxycarbonylamino-2-deoxy-beta -D-glucopyranose as donors and (2R)- or (2S)-2-azidohexadecanol derivatives as acceptors. Transformation of the azido glycosides into N-acylated products was done by a modified Staudinger reaction in the presence of fatty acyl chlorides. The four neoglycolipids are able to form a condensed monolayer at the air \ water interface; their pi -A isotherm diagrams are similar to that described for the natural glycosyl ceramides. The detailed analysis of the isotherms, taking into account the chirality of the lipid chains, allowed to determine the contribution of the different parts of the molecule under the monolayer packing. (C) 2001 Elsevier Science Ltd. All rights reserved.