(1S,2R,8R,8aS)-8-hydroxy-1,2-O-iso-propylideneoctahydro-1,2,8-indolizidine triol | 228098-81-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚里西啶
• 英文名称: (1S,2R,8R,8aS)-8-hydroxy-1,2-O-iso-propylideneoctahydro-1,2,8-indolizidine triol
• 英文别名: (1(S),2(R),8(R),8a(S))-1,2-O-Isopropylideneoctahydro-1,2,8-indolizidinetriol；(3aR,9R,9aS,9bS)-octahydro-2,2-dimethyl-[1,3]dioxolo[4,5-a]indolizin-9-ol；(1S,2R,8R,8aS)-1,2-O-Isopropylideneoctahydro-1,2,8-indolizidinetriol；(3aR,9R,9aS,9bS)-2,2-dimethyl-3a,4,6,7,8,9,9a,9b-octahydro-[1,3]dioxolo[4,5-a]indolizin-9-ol
• CAS: 228098-81-5
• 化学式: C₁₁H₁₉NO₃
• 分子量: 213.277
• InChiKey: HEVZREBCOASZGR-DOLQZWNJSA-N

物化性质

• 沸点：
  316.8±42.0 °C(Predicted)
• 密度：
  1.22±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  41.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1S,2R,8R,8aS)-8-hydroxy-1,2-O-iso-propylideneoctahydro-1,2,8-indolizidine triol 在 盐酸 作用下， 以 四氢呋喃 为溶剂， 以92%的产率得到(1S,2R,8R,8aS)-octahydro-1,2,8-indolizidinetriol
  参考文献：
  名称：

  从头不对称合成8a- epi- Swainsonine

  摘要：

  已从非手性糠醛开发了对映体选择性和非对映体控制的8a - epi - d- swainsonine方法。合成的关键步骤是一锅法，用于氢解除去两个保护基和两个分子内还原胺化反应。绝对立体化学是通过糠醛酮的不对称Noyori还原引入的。该途径依赖于非对映选择性钯催化的糖基化以安装异头键，以及Luche还原，非对映选择性二羟基化以建立吲哚并立定前体的甘露糖立体化学。

  DOI：

  10.1021/jo702476q
• 作为产物：
  描述：

  (1S,2R,8R,8aS)-8-hydroxy-1,2-(iso-propylidenedioxy)octahydro-5-indolizidinone 在 dimethyl sulfide borane 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以89%的产率得到(1S,2R,8R,8aS)-8-hydroxy-1,2-O-iso-propylideneoctahydro-1,2,8-indolizidine triol
  参考文献：
  名称：

  SmI 2介导的手性硝酮与酮/醛的还原偶联，对3,4-二羟基脯氨醇衍生物具有灵活的对映选择性

  摘要：

  描述了一种灵活的对映多羟基化脯氨醇衍生物的对映选择性方法，该方法基于io二碘化物介导的衍生自d-异抗坏血酸与醛/酮的手性硝酮（3 S，4 R）-8的还原偶联。因此，从芳族酮和脂族醛中获得多羟基脯氨醇衍生物9a – e和9h – j的产率高达65–91％。这些还原性羟烷基化在建立C-4立体异构中心时具有很高的非对映选择性。通过这种方式，（-）-8a- epi- swainsonine（4）和（-）-8,8a-di- Epi - swainsonine（5）已实现。

  DOI：

  10.1016/j.tet.2012.06.006

文献信息

• Asymmetric Routes Towards Polyfunctionalized Pyrrolidines: A Short Diastereoselective Synthesis of Polyhydroxylated Pyrrolidines and an Indolizidine
  作者：Bruno Dudot、Laurent Micouin、Isabelle Baussanne、Jacques Royer

  DOI：10.1055/s-1999-3434

  日期：1999.4

  Various (2S,3S,4R)-2-[(1R)-1-hydroxyalkyl]pyrrolidine-3,4-diols (11) have been prepared in 8 steps and 13-20% overall yields starting from (R)-(-)-phenylglycinol. This concise approach is based on the condensation of a chiral silyloxypyrrole with aldehydes which gave the (R,R)-aldol compounds in good yields and high diastereoselectivities. The cis-hydroxylation followed by reduction and deprotection gave the desired trihydroxylated pyrrolidines. The same strategy has been successively applied to a formal synthesis of 8a-epi-swainsonine.

  从(R)-(-)-苯甘氨醇出发，通过8步反应制备了各种(2S,3S,4R)-2-[(1R)-1-羟基烷基]吡咯烷-3,4-二醇(11)，总收率13-20%。这种简洁的方法是基于手性硅氧基吡咯与醛的缩合，从而得到(R,R)-醛缩化合物，收率高且立体选择性高。顺式羟基化后还原和脱保护得到所需的三羟基吡咯烷。同样的策略已成功应用于8a-表斯温森碱的正式合成。
• An acylnitroso cycloaddition approach to the synthesis of highly oxygenated indolizidine alkaloids
  作者：Gary E. Keck、Duane R. Romer

  DOI：10.1021/jo00074a040

  日期：1993.10

  A synthetic approach to the synthesis of highly oxygenated indolizidine alkaloids is described. A key feature of the approach is intramolecular [4 + 2] cycloaddition between an acylnitroso dienophile and a tethered diene moiety, followed by ring contraction of the 1,2-oxazine so formed to a pyrrolidine. The requisite intermediates were prepared in optically pure form froM L-glutamic acid.
• De Novo Asymmetric Synthesis of 8a-<i>epi</i>-Swainsonine
  作者：Jason N. Abrams、Ravula Satheesh Babu、Haibing Guo、Dianna Le、Jennifer Le、Joshua M. Osbourn、George A. O'Doherty

  DOI：10.1021/jo702476q

  日期：2008.3.1

  diastereocontrolled approach to 8a-epi-d-swainsonine has been developed from achiral furfural. The key step to this synthesis was a one-pot procedure for the hydrogenolytic removal of two protecting groups and two intramolecular reductive amination reactions. The absolute stereochemistry was introduced by asymmetric Noyori reduction of furfuryl ketone. This route relies on diastereoselective palladium-catalyzed

  已从非手性糠醛开发了对映体选择性和非对映体控制的8a - epi - d- swainsonine方法。合成的关键步骤是一锅法，用于氢解除去两个保护基和两个分子内还原胺化反应。绝对立体化学是通过糠醛酮的不对称Noyori还原引入的。该途径依赖于非对映选择性钯催化的糖基化以安装异头键，以及Luche还原，非对映选择性二羟基化以建立吲哚并立定前体的甘露糖立体化学。
• A flexible enantioselective approach to 3,4-dihydroxyprolinol derivatives by SmI2-mediated reductive coupling of chiral nitrone with ketones/aldehydes
  作者：Hong-Kui Zhang、Shou-Qiang Xu、Jia-Jia Zhuang、Jian-Liang Ye、Pei-Qiang Huang

  DOI：10.1016/j.tet.2012.06.006

  日期：2012.8

  derivatives was described, which is based on the samarium diiodide-mediated reductive coupling of the chiral nitrone (3S,4R)-8, derived from d-isoascorbic acid with aldehydes/ketones. Thereby, polyhydroxyprolinol derivatives 9a–e and 9h–j were obtained from aromatic ketones and aliphatic aldehydes in good to excellent yields of 65–91%. These reductive hydroxyalkylations are highly diastereoselective

  描述了一种灵活的对映多羟基化脯氨醇衍生物的对映选择性方法，该方法基于io二碘化物介导的衍生自d-异抗坏血酸与醛/酮的手性硝酮（3 S，4 R）-8的还原偶联。因此，从芳族酮和脂族醛中获得多羟基脯氨醇衍生物9a – e和9h – j的产率高达65–91％。这些还原性羟烷基化在建立C-4立体异构中心时具有很高的非对映选择性。通过这种方式，（-）-8a- epi- swainsonine（4）和（-）-8,8a-di- Epi - swainsonine（5）已实现。