isobutyl α-amicetoside | 75041-68-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: isobutyl α-amicetoside
• 英文别名: (2R,3S,6S)-2-methyl-6-(2-methylpropoxy)oxan-3-ol
• CAS: 75041-68-8；75041-69-9；96292-26-1；96292-27-2；96292-28-3；96292-29-4；102850-47-5
• 化学式: C₁₀H₂₀O₃
• 分子量: 188.267
• InChiKey: DHMBVXMLFUTNNJ-UTLUCORTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  isobutyl α-amicetoside 在 盐酸 作用下， 以 四氢呋喃 为溶剂， 反应 2.5h， 以98%的产率得到D-amicetose
  参考文献：
  名称：

  Synthesis of amicetose by three enantioselective methods

  摘要：

  Three methods for the synthesis of the deoxy sugar amicetose (2,3,6-trideoxy-D-erythro-hexopyranoside) are described. All three utilize the known dihydropyran 2-isobutoxy-6-methyl-2,3-dihydro-4H-pyran as an intermediate. Asymmetric hydroboration of the dihydropyran with IpcBH(2) gave enantiomerically enriched isobutyl ex and beta-amicetosides. Hydroboration with borane-tetrahydrofuran followed by derivatization of the major product (beta-anomer) with R-(-)-1-(1-naphthyl)ethylisocyanate gave diastereomeric carbamates which were separated and converted to isobutyl beta-D and beta-L-amicetosides having high optical purity. Racemic isobutyl beta-amicetosides were also resolved by enzymatic transesterification using lipase and an acyl transfer reagent. Porcine pancreatic lipase and lipases from Candida rugosa and Pseudomonas sp. were evaluated in the presence of either vinyl acetate, vinyl butyrate, or trifluoroethyl butyrate as acylating agents. A GC-based method for determining enantiomeric purity of amicetose derivatives was developed. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(97)00631-9
• 作为产物：
  描述：

  乙烯基异丁醚 在 sodium hydroxide 、 dimethyl sulfide borane 、 双氧水 、 对苯二酚 作用下， 反应 46.0h， 生成 isobutyl α-amicetoside
  参考文献：
  名称：

  dl-夹竹桃糖的高度非对映选择性合成

  摘要：

  从4-甲氧基-3-丁烯-2-酮与异丁基乙烯基醚之间的狄尔斯-阿尔德加合物开始，得到外消旋的夹竹桃糖（2,6-二脱氧-3-O-甲基-阿拉伯-己酮）通过硼氢化反应氧化异丁基β-和α-油酸的混合物。后者的反应是高度非对映选择性的，因为硼烷的攻击仅对OMe基团发生：没有形成非对映异构环核苷。唯一的副产物是在硼氢化步骤中发生的脱甲氧基化作用形成的少量异丁基β-和α-酰胺基。

  DOI：

  10.1016/0040-4020(82)80194-4

文献信息

• A highly diastereoselective synthesis of dl-oleandrose
  作者：G. Berti、G. Catelani、F. Colonna、L. Monti

  DOI：10.1016/0040-4020(82)80194-4

  日期：1982.1

  between 4-methoxy-3-buten-2-one and isobutyl vinyl ether, which was converted into a mixture of the isobutyl β- and α-oleandrosides through hydroboration-oxidation. The latter reaction is highly diastereoselective since attack by borane takes place exclusively anti to the OMe group: none of the diasteroisomeric cymarosides are formed. The only side-products are small amounts of the isobutyl β- and α-amicetodies

  从4-甲氧基-3-丁烯-2-酮与异丁基乙烯基醚之间的狄尔斯-阿尔德加合物开始，得到外消旋的夹竹桃糖（2,6-二脱氧-3-O-甲基-阿拉伯-己酮）通过硼氢化反应氧化异丁基β-和α-油酸的混合物。后者的反应是高度非对映选择性的，因为硼烷的攻击仅对OMe基团发生：没有形成非对映异构环核苷。唯一的副产物是在硼氢化步骤中发生的脱甲氧基化作用形成的少量异丁基β-和α-酰胺基。
• Preparation of isobutyl 3,4-anhydro-2, 6-dideoxy-DL-α-lyxo--hexopyranoside and its kinetic resolution with microsomal epoxide hydrolase
  作者：Pier Luigi Barili、Giancarlo Berti、Giorgio Catelani、Fabrizia Colonna、Ettore Mastrorilli、Marco Paoli

  DOI：10.1016/0040-4020(89)80154-1

  日期：1989.1

  same conditions the -anomer of 10 was stable. Complete hydrolysis of DL-3 with aqueous NaOH, or with microsomial epoxide hydrolase (MEH) gave exclusively the xylo-diol (isobutyl DL-α-boivinopyranoside 5). When the hydrolysis with MEH was stopped near 50% conversion and the product diol was separated from the unchanged epoxide, both were optically active, the former having the L and the latter the D

  从3-丁烯-2-酮与异丁基乙烯基醚之间的环加合物开始，按照涉及硼氢化-氧化，甲磺酰化的顺序，制备外消旋异丁基3,4-脱水-2,6-二脱氧-α-lyxo-己吡喃糖苷3 ，异头平衡，消除和环氧化。中间体2,3,4,6-四脱氧-α-3-DL-己基吡喃糖苷异丁基10在其制备所用的条件下（在DMSO中为t-BuOK）不稳定，部分转化为相应的2-己基吡喃糖苷。在相同条件下，10的端基是稳定的。DL-完全水解3用NaOH水溶液，或用microsomial环氧化物水解酶（MEH）得到专门的低聚木糖二醇（异丁基DL-α-boivinopyranoside 5）。当用MEH水解停止，转化率接近50％并且产物二醇与未改变的环氧化物分离时，两者都具有光学活性，前者具有L构型，而后者具有D构型。通过使用手性转移试剂，发现二醇和环氧化物的ee均至少为96％。
• Berti, Giancarlo; Catelani, Giorgio; Magi, Silvia, Gazzetta Chimica Italiana, 1980, vol. 110, # 2/3, p. 173 - 178
  作者：Berti, Giancarlo、Catelani, Giorgio、Magi, Silvia、Monti, Luigi

  DOI：——

  日期：——
• Berti, Giancarlo; Catelani, Giorgio; Colonna, Fabrizia, Gazzetta Chimica Italiana, <hi>1985</hi>, vol. 115, # 2, p. 85 - 90
  作者：Berti, Giancarlo、Catelani, Giorgio、Colonna, Fabrizia、Ferretti, Maria、Monti, Luigi

  DOI：——

  日期：——
• Synthesis of amicetose by three enantioselective methods
  作者：Lincoln A Noecker、Joseph A Martino、Paul J Foley、Diane M Rush、Robert M Giuliano、Frank J Villani

  DOI：10.1016/s0957-4166(97)00631-9

  日期：1998.1

  Three methods for the synthesis of the deoxy sugar amicetose (2,3,6-trideoxy-D-erythro-hexopyranoside) are described. All three utilize the known dihydropyran 2-isobutoxy-6-methyl-2,3-dihydro-4H-pyran as an intermediate. Asymmetric hydroboration of the dihydropyran with IpcBH(2) gave enantiomerically enriched isobutyl ex and beta-amicetosides. Hydroboration with borane-tetrahydrofuran followed by derivatization of the major product (beta-anomer) with R-(-)-1-(1-naphthyl)ethylisocyanate gave diastereomeric carbamates which were separated and converted to isobutyl beta-D and beta-L-amicetosides having high optical purity. Racemic isobutyl beta-amicetosides were also resolved by enzymatic transesterification using lipase and an acyl transfer reagent. Porcine pancreatic lipase and lipases from Candida rugosa and Pseudomonas sp. were evaluated in the presence of either vinyl acetate, vinyl butyrate, or trifluoroethyl butyrate as acylating agents. A GC-based method for determining enantiomeric purity of amicetose derivatives was developed. (C) 1998 Elsevier Science Ltd. All rights reserved.