(5S)-1-[(4S)-(2-oxo-4-phenyl-1,3-oxazolidin-3-yl)]-5-(triisopropylsilyloxy)-2-trimethylsilyloxy-3-azahexa-1,3-diene | 198147-93-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: (5S)-1-[(4S)-(2-oxo-4-phenyl-1,3-oxazolidin-3-yl)]-5-(triisopropylsilyloxy)-2-trimethylsilyloxy-3-azahexa-1,3-diene
• 英文别名: (5S)-1-[(4S)-2-oxo-4-phenyloxazolidin-3-yl]-2-trimethylsilyloxy-3-aza-5-triisopropylsilyloxyhexa-1Z,3E-diene；(5S)-1-[(4S)-2-oxo-4-phenyloxazolidin-3-yl]-2-trimethylsilyloxy-3-aza-5-triisopropylsilyloxy-hexa-1,3-diene；(4S)-4-phenyl-3-[(Z)-2-trimethylsilyloxy-2-[(E)-[(2S)-2-tri(propan-2-yl)silyloxypropylidene]amino]ethenyl]-1,3-oxazolidin-2-one
• CAS: 198147-93-2
• 化学式: C₂₆H₄₄N₂O₄Si₂
• 分子量: 504.817
• InChiKey: YSLUUOCSOPUMGQ-DUODVLAHSA-N

物化性质

• 沸点：
  492.5±55.0 °C(predicted)
• 密度：
  1.01±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.48
• 重原子数：
  34
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  60.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (5S)-1-[(4S)-(2-oxo-4-phenyl-1,3-oxazolidin-3-yl)]-5-(triisopropylsilyloxy)-2-trimethylsilyloxy-3-azahexa-1,3-diene 在 三氟化硼乙醚 、 lithium 作用下， 以 四氢呋喃 、 二氯甲烷 、 氨 、 水 、 丙酮 、 叔丁醇 为溶剂， 反应 4.03h， 生成 [(2R,5R)-4-oxo-2-[(1S)-triisopropylsilanyloxyethyl]-[1,3]oxazinan-5-yl]carbamic acid benzyl ester
  参考文献：
  名称：

  Enantioselective synthesis of protected d-serine from tetrahydrooxazin-4-one via a hetero Diels–Alder reaction

  摘要：

  Hetero Diels-Alder reaction between 2-aza-3-trimethylsilyloxy-1,3-diene and aldehydes gives rise to tetrahydrooxazin-4-ones, useful intermediates in the synthesis of alpha-amino-beta-hydroxy acids. Herein we report the complete stereoselective synthesis of D-serine Cbz-methyl ester. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00536-0
• 作为产物：
  描述：

  (S)-(+)-2-氧代-4-苯基-3-恶唑烷乙酸 在 草酰氯 、 三乙胺 作用下， 以 正庚烷 、 甲苯 为溶剂， 反应 4.5h， 生成 (5S)-1-[(4S)-(2-oxo-4-phenyl-1,3-oxazolidin-3-yl)]-5-(triisopropylsilyloxy)-2-trimethylsilyloxy-3-azahexa-1,3-diene
  参考文献：
  名称：

  Hetero Diels−Alder vs Electrocyclic Reaction of Azadiene:  Selective Synthesis of All Stereoisomers of Threonines

  摘要：

  DOI：

  10.1021/jo971395g

文献信息

• Stereochemical Aspects of a Two-Step Staudinger Reaction − Asymmetric Synthesis of Chiral Azetidine-2-ones
  作者：Alessandro Bongini、Mauro Panunzio、Giovanni Piersanti、Elisa Bandini、Giorgio Martelli、Giuseppe Spunta、Alessandro Venturini

  DOI：10.1002/1099-0690(200007)2000:13<2379::aid-ejoc2379>3.0.co;2-f

  日期：2000.7

  well as reaction conditions. Ab initio studies at MP2/6−31G* and QCISD(T)/6−311G** levels on model compounds provide a rationalization of the experimental results obtained. From the experimental as well as theoretical data it is clear that the presence of the silyl enol group in the intermediate azadiene is crucial in its stabilisation and plays a fundamental role in the conrotatory ring closure and,

  N-三烷基甲硅烷基亚胺与多种甘氨酸衍生的烯酮反应产生 1,3-氮杂二烯，在某些情况下已对其进行分离和表征。这些化合物的旋转闭环导致形成氮杂环丁烷-2-酮，从而允许正式的两步施陶丁格反应。观察到排他的反式非对映选择性。获得了不太严格的非对映面选择性。已经进行了一组实验以评估结构参数和反应条件的影响。在 MP2/6-31G* 和 QCISD(T)/6-311G** 水平对模型化合物进行的从头算研究提供了对所获得实验结果的合理化。
• An efficient synthesis of the cyclic form of scalemic 2,4-di-epi-polyoxamic acid exploiting the hetero Diels-Alder approach
  作者：Elisa Bandini、Giorgio Martelli、Giuseppe Spunta、Alessandro Bongini、Mauro Panunzio、Giovanni Piersanti

  DOI：10.1016/s0957-4166(97)00530-2

  日期：1997.11

  An efficient synthesis of the lactonic derivative of 2,4-di-epi- polyoxamic acid, in high enantiomeric purity, through a hetero Diels-Alder approach, is reported.

  据报道，通过杂Diels-Alder方法，可以高效合成高对映体纯度的2,4-二-表-聚草酰胺酸的内酯衍生物。
• Synthesis of perhydroxazin-4-ones. Competitive Mukaiyama versus hetero Diels–Alder reaction in the cycloaddition of 2-aza-3-trimethylsilyloxy-1,3-butadiene and aldehydes
  作者：Alessandro Bongini、Mauro Panunzio、Elisa Bandini、Eileen Campana、Giorgio Martelli、Giuseppe Spunta

  DOI：10.1016/s0957-4166(01)00051-9

  日期：2001.3

  The reactions of 2-aza-3-trimethylsilyloxy-1,3-butadiene with carbonyl dienophiles are described. 2-Aza-1,3-butadienes participate as dienes in the [4+2] cycloaddition with aldehydes to afford perhydroxazin-4-ones in good yields. Experimental results, however, show that a Mukaiyama type two-step reaction must be taken into account. The cycloadducts obtained have proved to be useful intermediates in the synthesis of alpha -amino-beta -hydroxy acids. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Lewis acid-catalyzed electrocyclization of 2-aza-1,3-butadienes to NH-β-lactams
  作者：Alessandro Bongini、Mauro Panunzio、Emiliano Tamanini、Giorgio Martelli、Paola Vicennati、Magda Monari

  DOI：10.1016/s0957-4166(03)00162-9

  日期：2003.4

  Lewis acid-catalyzed cyclization of 2-aza-3-trimethylsilytoxy-buta-1,3-diene is reported.. Stereochemical differences with the uncatalyzed cyclization are discussed. (C) 2003 Elsevier Science Ltd. All rights reserved.
• Solution phase library of perhydrooxazin-4-ones
  作者：Mauro Panunzio、Marzia Villa、Andrea Missio、Tino Rossi、Pierfausto Seneci

  DOI：10.1016/s0040-4039(98)01372-0

  日期：1998.9

  A general approach to the solution phase parallel synthesis of perhydrooxazin-4-ones, which allows the preparation of milligram quantities of each individual member, is reported. An efficient purification; method, using as "Sequestration Enabling Reagent" (SER) aminomethylpolystyrene resin in the presence of trimethylorthoformate is also described. (C) 1998 Elsevier Science Ltd. All rights reserved.