(3R,8R,8aR)-8-allyl-5-oxo-3-phenyl-2,3,6,7,8,8a-hexahydro-5H-oxazolo[3,2-a]pyridine | 864967-32-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: (3R,8R,8aR)-8-allyl-5-oxo-3-phenyl-2,3,6,7,8,8a-hexahydro-5H-oxazolo[3,2-a]pyridine
• 英文别名: (3R,8R,8aR)-3-phenyl-8-prop-2-enyl-2,3,6,7,8,8a-hexahydro-[1,3]oxazolo[3,2-a]pyridin-5-one
• CAS: 864967-32-8
• 化学式: C₁₆H₁₉NO₂
• 分子量: 257.332
• InChiKey: PMYGJYVSRFHLDF-OFQRWUPVSA-N

物化性质

• 沸点：
  417.8±34.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3R,8R,8aR)-8-allyl-5-oxo-3-phenyl-2,3,6,7,8,8a-hexahydro-5H-oxazolo[3,2-a]pyridine 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) copper(l) iodide 、 三甲基氯硅烷 、 lithium chloride 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 (3R,6aR,10aS,10bR)-6-(methoxycarbonyl)-5-oxo-3-phenyl-2,3,6,6a,7,10,10a,10b-octahydro-5H-oxazolo[2,3-a]isoquinoline
  参考文献：
  名称：

  An Enantioselective Entry to cis-Perhydroisoquinolines

  摘要：

  [GRAPHICS]An enantioselective route to cis-perhydroisoquinolines, involving a cycloconclensation reaction of (R)-phenylglycinol with a racemic oxoester, a stereoselective conjugate addition to an unsaturated bicyclic lactam, and the closure of the carbocyclic ring by a ring-closing metathesis as the key steps is reported. This route allows the preparation of 3-cyano derivatives as well as cis-octahydroisoquinolines bearing a quaternary center at the N-position.

  DOI：

  10.1021/ol051242c
• 作为产物：
  描述：

  methyl 4-formyl-6-heptenoate 、 D-苯甘氨醇 在 sodium sulfate 作用下， 以 乙醚 为溶剂， 反应 1.0h， 以71%的产率得到(3R,8R,8aR)-8-allyl-5-oxo-3-phenyl-2,3,6,7,8,8a-hexahydro-5H-oxazolo[3,2-a]pyridine
  参考文献：
  名称：

  动态动力学拆分和去对称化过程：哌啶的对映选择性合成的直接方法。

  摘要：

  报道了合成对映纯多取代哌啶的简单方法。它涉及直接产生已经在杂环上掺入碳取代基的手性非外消旋恶唑并[3，2-a]哌啶酮内酰胺，随后除去手性助剂。关键步骤是（R）-苯基甘醇或其他氨基醇与外消旋或手性δ-氧代（二）酸衍生物在高度立体选择性的过程中进行的环缩合反应，该过程涉及动态动力学拆分和/或非对映体或对映体酯基的去对称化。

  DOI：

  10.1002/chem.200600420

文献信息

• A general synthetic route to enantiopure cis-fused perhydrocycloalka[c]pyridines from phenylglycinol-derived lactams
  作者：Mercedes Amat、Maria Pérez、Annamaria T. Minaglia、Bruno Peretto、Joan Bosch

  DOI：10.1016/j.tet.2007.01.072

  日期：2007.6

  A synthetic route to enantiopure piperidines bearing a five-, six-, or seven-membered carbocyclic ring cis-fused on the c side of the heterocycle from a common phenylglycinol-derived δ-lactam is reported. Key steps are (i) a cyclocondensation reaction of (R)-phenylglycinol with a racemic γ-oxoester in a process that involves a dynamic kinetic resolution; (ii) a highly stereoselective conjugate addition

  据报道，从普通的苯甘醇衍生的δ-内酰胺到杂环的c端带有5、6或7元碳环顺式稠合的对映纯哌啶的合成路线已被报道。关键步骤是（i）（R）-苯基甘氨醇与外消旋γ-氧代酸酯的环缩合反应，该过程涉及动态动力学拆分；（ii）将有机铜酸酯高度立体选择性地共轭加成到不饱和δ-内酰胺上；（iii）闭环烯烃复分解。
• Total Synthesis of (+)-Madangamine D
  作者：Roberto Ballette、Maria Pérez、Stefano Proto、Mercedes Amat、Joan Bosch

  DOI：10.1002/anie.201402263

  日期：2014.6.10

  Madangamines are a group of bioactive marine sponge alkaloids, embodying an unprecedented diazapentacyclic skeletal type. The enantioselective total synthesis of madangamine D has been accomplished, and represents the first total synthesis of an alkaloid of the madangamine group. It involves the stereoselective construction of the diazatricyclic ABC core using a phenylglycinol‐derived lactam as the starting

  Madangamines是一组具有生物活性的海洋海绵生物碱，体现了前所未有的二氮杂五环骨架类型。已经完成了对马丹胺D的对映选择性全合成，并且代表了对马丹胺基团的生物碱的第一个全合成。它涉及使用苯甘氨醇衍生的内酰胺作为起始对映体支架和随后大环外围环组装的二氮三环ABC核的立体选择性构建。该合成首次提供了马丹胺D的纯样品，并证实了该生物碱家族的绝对构型。
• First Enantioselective Synthesis of the Diazatricyclic Core of Madangamine Alkaloids
  作者：Mercedes Amat、Maria Pérez、Stefano Proto、Teresa Gatti、Joan Bosch

  DOI：10.1002/chem.201000421

  日期：2010.8.16

  En route to madangamines: A unified strategy has been developed for the enantioselective assembly of functionalized diazatricyclic synthetic precursors of madangamines (see scheme; Bn=benzyl, Boc=tert‐butoxycarbonyl, Mbs=para‐methoxybenzenesulfonyl).

  前往madangamines的途中：已开发出统一的策略，用于对madangamines的功能化二氮三环合成前体进行对映选择性组装（参见方案; Bn =苄基，Boc =叔丁氧羰基，Mbs =对甲氧基苯磺酰基）。
• Enantioselective formal synthesis of (+)-madangamine A
  作者：Celeste Are、Maria Pérez、Joan Bosch、Mercedes Amat

  DOI：10.1039/c9cc03690c

  日期：——

  An enantioselective formal synthesis of the marine alkaloid madangamine A using phenylglycinol-derived lactam 1 as the starting enantiomeric scaffold is reported. The synthesis involves the construction of the C-9 substituted diazatricyclic ABC core and the final closure of D and E rings from the polyunsaturated skipped intermediate 19.

  报道了使用衍生自苯基甘醇的内酰胺1作为起始对映体骨架的海洋生物碱马达加胺A的对映体选择性形式合成。合成涉及C-9取代的二氮杂三环ABC核的构建以及D和E环从多不饱和跳过中间体19的最终闭合。
• Stereocontrolled synthesis of enantiopure cis- and trans-3,4,4a,5,8,8a-hexahydro-1H-quinolin-2-ones
  作者：Mercedes Amat、Maria Pérez、Annamaria T. Minaglia、Daniele Passarella、Joan Bosch

  DOI：10.1016/j.tetasy.2008.10.007

  日期：2008.10

  Starting from the 8-allyl substituted oxazolopiperidone lactam 2b, which is easily accessible from (R)-phenylglycinol and racemic delta-oxoester 1a, two-step sequences involving a stereciselective alpha-amidoalkylation reaction, either with inversion or retention Of configuration, followed by a ring-closing metathesis, provide diastereodivergent routes to enantiopure cis- and trans-3,4,4a,5,8,8a-hexahydro-1H-quinolin-2-ones. (C) 2008 Elsevier Ltd. All rights reserved.