(8SR,8aRS)-hexahydro-8-hydroxy-3(2H)-indolizinone | 139745-93-0

• 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: (8SR,8aRS)-hexahydro-8-hydroxy-3(2H)-indolizinone
• 英文别名: (±)-8-hydroxyhexahydroindolizin-3(5H)-one；(+/-)-(8S,8aR)-8-hydroxy-hexahydroindolizin-3(5H)-one；(8S,8aR)-8-hydroxy-2,5,6,7,8,8a-hexahydro-1H-indolizin-3-one
• CAS: 139745-93-0
• 化学式: C₈H₁₃NO₂
• 分子量: 155.197
• InChiKey: KTABOEKIAVLJNW-RQJHMYQMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  40.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (8SR,8aRS)-hexahydro-8-hydroxy-3(2H)-indolizinone 在 dimethyl sulfide borane 作用下， 以85%的产率得到cis-8-hydroxyindolizidine
  参考文献：
  名称：

  氨基酸作为吲哚并立定生物碱的前体。DPPA促进的双环氨基酸脱羰作用：容易进入羟基吲哚并咪唑

  摘要：

  描述了通过两种替代途径由（D，L）-哌啉酸合成8，8a-反式-8-羟基-吲哚并立核苷12。二叠氮基磷酸二苯酯（DPPA）促进的双环羧酰胺9的立体有择脱羰作用是我们策略的关键步骤。双环烯酰胺10被描述为羟基化吲哚唑烷合成中的有价值的中间体。

  DOI：

  10.1016/s0040-4039(00)78513-3
• 作为产物：
  描述：

  N-allyl-4-pentynamide 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 bis-triphenylphosphine-palladium(II) chloride 、 sodium tetrahydroborate 、 copper(l) iodide 、 palladium 10% on activated carbon 、 氢气 、 三乙胺 、 [双(三氟乙酰氧基)碘]苯 、 zinc(II) chloride 作用下， 以 甲醇 、 2,2,2-三氟乙醇 、 甲苯 为溶剂， -78.0~80.0 ℃ 、482.64 kPa 条件下， 反应 20.5h， 生成 (8SR,8aRS)-hexahydro-8-hydroxy-3(2H)-indolizinone
  参考文献：
  名称：

  Application of the intramolecular PIFA-mediated amidation of alkynes to the synthesis of substituted indolizidinones

  摘要：

  The construction of the title compounds has been achieved from properly substituted linear alkynylamides through the suitable combination of two key cyclization steps. First, an intramolecular PIFA-mediated alkyne amidation protocol leads to the creation of the pyrrolidinone nucleus, which under proper manipulation of the generated keto carbonyl group permits the assembling of the indolizidinone skeleton by the introduction of a subsequent ring closing olefin metathesis step. Finally, its transformation into a series of substituted mono- and trihydroxylated indolizidinone derivatives is achieved by manipulation of the remaining unsaturated fragment under hydrogenation and dihydroxylation conditions. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.03.033

文献信息

• Metal-Free Decarboxylative Hetero-Diels–Alder Synthesis of 3-Hydroxypyridines: A Rapid Access to <i>N</i>-Fused Bicyclic Hydroxypiperidine Scaffolds
  作者：Laurie-Anne Jouanno、Vincent Di Mascio、Vincent Tognetti、Laurent Joubert、Cyrille Sabot、Pierre-Yves Renard

  DOI：10.1021/jo402729a

  日期：2014.2.7

  A complete experimental and theoretical study of the thermally controlled metal-free decarboxylative hetero-Diels–Alder (HDA) reaction of 5-alkoxyoxazoles with acrylic acid is reported. This strategy offers a new entry to valuable 2,6-difunctionalized 3-hydroxypyridines from readily available 2- and 4-disubstituted 5-alkoxyoxazoles. The reaction conditions proved compatible with, among others, ketone

  报道了5-烷氧基恶唑与丙烯酸热控制的无金属脱羧杂狄尔斯-阿尔德（HDA）反应的完整实验和理论研究。该策略为易于获得的2-和4-二取代的5-烷氧基恶唑提供了有价值的2,6-二官能化的3-羟基吡啶的新入口。证明该反应条件尤其与酮，酰胺，酯，醚和腈基相容。该方案具有广泛的官能团耐受性，可通过吡啶脱芳构化策略快速而通用地获得羟基吲哚并咪唑和羟基喹oli嗪衍生物。
• Synthesis and Binding Properties to GABA Receptors of 3-Hydroxypyridinyl- and 3-Hydroxypiperidinyl-Analogues of Baclofen
  作者：Nicoletta Desideri、Alessandro Galli、Isabella Sestili、Maria Luisa Stein

  DOI：10.1002/ardp.19923250108

  日期：——

  The synthesis of 3‐(3‐hydroxy‐2‐pyridinyl)propanoic acid, 3‐(3‐hydroxy‐2‐pyridinyl)‐4‐aminobutanoic acid, their corresponding piperidine compounds, and of some cyclized derivatives is described.

  描述了 3-(3-羟基-2-吡啶基)丙酸、3-(3-羟基-2-吡啶基)-4-氨基丁酸、它们相应的哌啶化合物和一些环化衍生物的合成。
• Decarbonylation of α-tertiary amino acids application to the synthesis of polyhydroxylated indolizidines from D,L-pipecolic acid
  作者：María J. Martín-López、Rosa Rodriguez、Francisco Bermejo

  DOI：10.1016/s0040-4020(98)00689-9

  日期：1998.9

  The decarbonylation of the bicyclic α-tertiary carboxamido acid 11 led to the enamide 12, easily transformed into the indolizidine alkaloid 8,8a-trans-8-hydroxy-indolizidine 14. Likewise, the same process applied to the α-substituted pipecolic acid derivative 5 led to the unsaturated ester 6 which was easily transformed either into δ-coniceine 9 or to 14. The thermal fragmentation of the acyl derivative

  双环α-叔羧酰胺酸11的脱羰基导致酰胺12，轻松转化为吲哚并立生物碱8,8a-反式-8-羟基吲哚并立胺14。同样，对α-取代的胡椒酸衍生物5进行相同的处理，得到不饱和酯6，该不饱和酯6容易转化为δ-可卡因9或14。酰基衍生物22的热裂解产生了已转化为（±）-swainsonine 26的烯酰胺24。
• SmI₂-Mediated Radical Cross-Couplings of α-Hydroxylated Aza-hemiacetals and<i>N</i>,<i>S</i>-Acetals with α,β-Unsaturated Compounds: Asymmetric Synthesis of (+)-Hyacinthacine A₂, (−)-Uniflorine A, and (+)-7-<i>epi</i>-Casuarine
  作者：Xue-Kui Liu、Shi Qiu、Yong-Gang Xiang、Yuan-Ping Ruan、Xiao Zheng、Pei-Qiang Huang

  DOI：10.1021/jo200600n

  日期：2011.6.17

  The SmI2-mediated radical coupling reactions of beta-hydroxylated pyrrolidine/piperidine aza-hemiacetals 8 and 9 and N,S-acetals 6 and 33 with alpha/beta-unsaturated compounds are described. This method allows a rapid access to beta-hydroxylated pyrrolidines, piperidines, pyrrolizidinones, and indolizidinones. Starting from N,S-acetal 33 and via a common intermediate 27, the alkaloids hyacinthacine A(2) (2), uniflorine A (3, 6-epi-casuarine), and the unnatural epimer 7-epi-casuarine (37) have been synthesized in four and five steps with overall yields of 34%, 16%, and 13%, respectively. The radical mechanism of the coupling reactions has been confirmed by controlled experiments, which also allowed deducing the anionic mechanism in the coupling between N,S-acetal 6 and carbonyl compounds. This demonstrates that the mechanisms of these SmI2-mediated reactions are switchable from Barbier-type anionic to radical by cooperative action of BF3 center dot OEt2 and t-BuOH.