benzyl (3R,8S,8aR)-8-ethyl-5-oxo-3-phenyl-2,3,8,8a-tetrahydro-[1,3]oxazolo[3,2-a]pyridine-6-carboxylate | 331473-26-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: benzyl (3R,8S,8aR)-8-ethyl-5-oxo-3-phenyl-2,3,8,8a-tetrahydro-[1,3]oxazolo[3,2-a]pyridine-6-carboxylate
• CAS: 331473-26-8
• 化学式: C₂₃H₂₃NO₄
• 分子量: 377.44
• InChiKey: ZDWMWLPVDHBMKV-RBDMOPTHSA-N

物化性质

• 沸点：
  582.6±50.0 °C(Predicted)
• 密度：
  1.25±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  55.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  benzyl (3R,8S,8aR)-8-ethyl-5-oxo-3-phenyl-2,3,8,8a-tetrahydro-[1,3]oxazolo[3,2-a]pyridine-6-carboxylate 在 lithium chloride copper(l) iodide 、 重铬酸吡啶 、 三甲基氯硅烷 、 臭氧 、 苯基锂 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 (3R,7R,8S,8aR)-7-Carboxymethyl-8-ethyl-5-oxo-3-phenyl-hexahydro-oxazolo[3,2-a]pyridine-6-carboxylic acid benzyl ester
  参考文献：
  名称：

  Stereodivergent Synthesis of Enantiopure cis- and trans-3-Ethyl-4-piperidineacetates

  摘要：

  [GRAPHICS]Starting from a common chiral bicyclic lactam 11, enantiopure trans- or cis-3-ethyl-4-piperidineacetate derivatives are obtained by conjugate addition of an enolate or a cuprate to the unsaturated lactams 12 or 18, respectively.

  DOI：

  10.1021/ol0263245
• 作为产物：
  描述：

  (3R,8S,8aR)-8-ethyl-5-oxo-3-phenyl-2,3,6,7,8,8a-hexahydro-5H-oxazolo[3,2-a]pyridine 在 氧气 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 0.83h， 生成 benzyl (3R,8S,8aR)-8-ethyl-5-oxo-3-phenyl-2,3,8,8a-tetrahydro-[1,3]oxazolo[3,2-a]pyridine-6-carboxylate
  参考文献：
  名称：

  将有机铜酸盐加到手性双环δ-内酰胺中。顺式-3,4-二取代和3,4,5-三取代的哌啶的对映选择性合成。

  摘要：

  [反应：见正文]手性非外消旋双环内酰胺3，可通过（R）-苯基甘氨醇和外消旋4-甲酰基己酸酯的环脱水反应轻松获得，被转化为不饱和内酰胺5，内酰胺5经过立体选择性共轭添加了低级的氰尿酸酯，最终导致对映体纯的顺式-3,4-二取代和3,4,5-三取代的哌啶。

  DOI：

  10.1021/ol007010p

文献信息

• A Synthetic Approach to Ervatamine-Silicine Alkaloids. Enantioselective Total Synthesis of (−)-16-Episilicine
  作者：Mercedes Amat、Núria Llor、Begoña Checa、Elies Molins、Joan Bosch

  DOI：10.1021/jo902346j

  日期：2010.1.1

  Starting from an appropriate unsaturated phenylglycinol-derived oxazolopiperidone lactam, the synthesis of (−)-16-episilicine is reported, the key steps being a stereoselective conjugate addition, a stereoselective alkylation, and a ring-closing metathesis reaction. This represents the first enantioselective total synthesis of an alkaloid of the silicine group.

  从合适的不饱和苯基甘醇衍生的恶唑并哌啶酮内酰胺开始，据报道合成了（-）-16-哌啶子碱，关键步骤是立体选择性共轭加成，立体选择性烷基化和闭环易位反应。这代表了硅基生物碱的第一个对映选择性全合成。
• Conjugate Addition of 2-Acetylindole Enolates to Unsaturated Oxazolopiperidone Lactams: Enantioselective Access to the Tetracyclic Ring System of Ervitsine
  作者：Mercedes Amat、Begoña Checa、Núria Llor、Maria Pérez、Joan Bosch

  DOI：10.1002/ejoc.201001020

  日期：2011.2

  Dedicated to Prof. Carmen Najera on the occasion of her 60th birthday The stereochemical outcomes of the conjugate addition reac- tions of 2-acetylindole enolates to the unsaturated phenylgly- cinol-derived oxazolopiperidone lactams 1a-f have been studied. After reduction of the 2-acylindole carbonyl group,

  献给 Carmen Najera 教授 60 岁生日 2-乙酰吲哚烯醇化物与不饱和苯基甘氨醇衍生的恶唑哌啶酮内酰胺 1a-f 的共轭加成反应的立体化学结果已被研究。2-酰基吲哚羰基还原后，
• An Unexpected Oxidation in the Generation of Cyclopenta[<i>c</i>]piperidines by Ring-Closing Metathesis
  作者：Mercedes Amat、Elisa Brunaccini、Begoña Checa、Maria Pérez、Núria Llor、Joan Bosch

  DOI：10.1021/ol901704f

  日期：2009.10.1

  Ring-closing metathesis reaction of dienes A (n = 1, R = CO2R') leads to fused cyclopentenones C instead of the expected cyclopentene derivatives B. RCM reaction of the other dienes A takes place satisfactorily, affording the expected fused cycloalkene derivatives B. Cyclohexene B (n = 2, R = CO2R') also undergoes oxidation to the corresponding cyclohexenone C.
• Stereodivergent Synthesis of Enantiopure <i>cis</i>- and <i>trans</i>-3-Ethyl-4-piperidineacetates
  作者：Mercedes Amat、Maria Pérez、Núria Llor、Joan Bosch

  DOI：10.1021/ol0263245

  日期：2002.8.1

  [GRAPHICS]Starting from a common chiral bicyclic lactam 11, enantiopure trans- or cis-3-ethyl-4-piperidineacetate derivatives are obtained by conjugate addition of an enolate or a cuprate to the unsaturated lactams 12 or 18, respectively.
• Conjugate Addition of Organocuprates to Chiral Bicyclic δ-Lactams. Enantioselective Synthesis of <i>cis</i>-3,4-Disubstituted and 3,4,5-Trisubstituted Piperidines
  作者：Mercedes Amat、Maria Pérez、Núria Llor、Joan Bosch、Elena Lago、Elies Molins

  DOI：10.1021/ol007010p

  日期：2001.2.1

  [reaction: see text] Chiral nonracemic bicyclic lactam 3, easily accessible by cyclodehydration of (R)-phenylglycinol and racemic methyl 4-formylhexanoate, was converted to the unsaturated lactams 5, which undergo the stereoselective conjugate addition of lower order cyanocuprates to ultimately lead to enantiopure cis-3,4-disubstituted and 3,4,5-trisubstituted piperidines.

  [反应：见正文]手性非外消旋双环内酰胺3，可通过（R）-苯基甘氨醇和外消旋4-甲酰基己酸酯的环脱水反应轻松获得，被转化为不饱和内酰胺5，内酰胺5经过立体选择性共轭添加了低级的氰尿酸酯，最终导致对映体纯的顺式-3,4-二取代和3,4,5-三取代的哌啶。