(5S,6R)-4,5-dimethyl-6-phenyl-3-propionyl-3,4,5,6-tetrahydro-2H-1,3,4-oxadiazin-2-one | 397332-07-9

• 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: (5S,6R)-4,5-dimethyl-6-phenyl-3-propionyl-3,4,5,6-tetrahydro-2H-1,3,4-oxadiazin-2-one
• 英文别名: N₃-propionyl-3,4,5,6-tetrahydro-2H-1,3,4-oxadiazin-2-one；(5S,6R)-4,5-dimethyl-6-phenyl-3-propanoyl-1,3,4-oxadiazinan-2-one
• CAS: 397332-07-9
• 化学式: C₁₄H₁₈N₂O₃
• 分子量: 262.309
• InChiKey: TYXWFBPLRUKPNL-GWCFXTLKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  49.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  苄氧基乙醛 、 (5S,6R)-4,5-dimethyl-6-phenyl-3-propionyl-3,4,5,6-tetrahydro-2H-1,3,4-oxadiazin-2-one 在 四氯化钛 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 4.42h， 以76%的产率得到(5S,6R)-3-(4-benzyloxy-3-hydroxy-2-methylbutyryl)-3,4,5,6-tetrahydro-4,5-dimethyl-6-phenyl-1,3,4-oxadiazin-2-one
  参考文献：
  名称：

  An improved procedure for the asymmetric aldol reaction of the titanium enolate of an N3-propionyl-3,4,5,6-tetrahydro-2H-1,3,4-oxadiazin-2-one

  摘要：

  The direct formation of the titanium enolate of N-3-propionyl-3,4,5.6-tetrahydro-2H-1,3,4-oxadiazin-2-one has been achieved through complexation with titanium tetrachloride at 25degreesC, followed by deprotonation with triethylamine (-78 to 25degreesC). The preformed titanium enolate has been reacted with D2O/DCl to afford deuterated derivative 6 and also reacted with a series of aromatic and aliphatic aldehydes affording aldol adducts 4a-f with crude diastereoselectivities ranging from 8: 1 to 38:1. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(03)00043-0
• 作为产物：
  描述：

  麻黄碱 在 盐酸 、 lithium aluminium tetrahydride 、 lithium hydride 、 sodium nitrite 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 生成 (5S,6R)-4,5-dimethyl-6-phenyl-3-propionyl-3,4,5,6-tetrahydro-2H-1,3,4-oxadiazin-2-one
  参考文献：
  名称：

  走向结构新型手性助剂的发展：（1R，2S）-麻黄碱为基础的3,4,5,6-四氢-2H-1,3,4-恶二嗪-2-one的非对映选择性羟醛反应。

  摘要：

  [反应：见正文]已经用（1R，2S）-麻黄碱衍生的3,4,5,6-四氢-2H-1,3,4-恶二嗪-2-酮（2）进行了不对称的羟醛加成反应。非对映异构体形成非Evans粗加合物8a-h的非对映选择性为75:25至99：1。烯醇化物的面部选择性由立体异构的N（4）-甲基取代基指示。羟醛加合物8a容易通过酸水解裂解，得到（95％ee）的（2S，3S）-3-羟基-2-甲基-3-苯基丙酸（9）。

  DOI：

  10.1021/ol026721f

文献信息

• X-Ray crystallographic and 13C nuclear magnetic resonance studies of 3,4,5,6-tetrahydro-2H-1,3,4-oxadiazin-2-ones derived from ephedrine and pseudoephedrine
  作者：Shawn R Hitchcock、George P Nora、David M Casper、Michael D Squire、Christopher D Maroules、Gregory M Ferrence、Lisa F Szczepura、Jean M Standard

  DOI：10.1016/s0040-4020(01)00967-x

  日期：2001.12

  2S)-pseudoephedrine have been synthesized and their conformational properties have been examined. The ephedrine heterocycles 5–7a appear to favor one set of equilibrating conformers while the pseudoephedrine heterocycles 5–7b exist as multiple conformers at room temperature. The observed conformational behavior of these heterocycles is attributed to allylic strain and a gauche effect arising from the torsional energy

  合成了由（1 R，2 S）-麻黄碱和（1 S，2 S）-伪麻黄碱衍生的3,4,5,6-四氢-2 H -1,3,4-恶二嗪-2-酮，并合成了它们构象性质已被检查。麻黄碱杂环5 -图7a显示以有利于一组平衡构象异构体，而假麻黄碱杂环5 - 7b中存在作为在室温下的多个构象异构体。观察到的这些杂环的构象行为归因于烯丙基应变和N 3-和N 4的孤对电子之间的扭转能垒引起的变态效应。-氮。
• An improved procedure for the asymmetric aldol reaction of the titanium enolate of an N3-propionyl-3,4,5,6-tetrahydro-2H-1,3,4-oxadiazin-2-one
  作者：David M. Casper、Shawn R. Hitchcock

  DOI：10.1016/s0957-4166(03)00043-0

  日期：2003.2

  The direct formation of the titanium enolate of N-3-propionyl-3,4,5.6-tetrahydro-2H-1,3,4-oxadiazin-2-one has been achieved through complexation with titanium tetrachloride at 25degreesC, followed by deprotonation with triethylamine (-78 to 25degreesC). The preformed titanium enolate has been reacted with D2O/DCl to afford deuterated derivative 6 and also reacted with a series of aromatic and aliphatic aldehydes affording aldol adducts 4a-f with crude diastereoselectivities ranging from 8: 1 to 38:1. (C) 2003 Elsevier Science Ltd. All rights reserved.
• Toward the Development of a Structurally Novel Class of Chiral Auxiliaries:  Diastereoselective Aldol Reactions of a (1<i>R</i>,2<i>S</i>)-Ephedrine-Based 3,4,5,6-Tetrahydro-2<i>H</i>-1,3,4-oxadiazin-2-one
  作者：David M. Casper、James R. Burgeson、Joel M. Esken、Gregory M. Ferrence、Shawn R. Hitchcock

  DOI：10.1021/ol026721f

  日期：2002.10.1

  [reaction: see text] Asymmetric aldol addition reactions have been conducted with (1R,2S)-ephedrine-derived 3,4,5,6-tetrahydro-2H-1,3,4-oxadiazin-2-one (2). Diastereoselectivities range from 75:25 to 99:1 for the formation of the crude non-Evans syn adducts 8a-h. The facial selectivity of the enolate is directed by the stereogenic N(4)-methyl substituent. Aldol adduct 8a is readily cleaved by acid

  [反应：见正文]已经用（1R，2S）-麻黄碱衍生的3,4,5,6-四氢-2H-1,3,4-恶二嗪-2-酮（2）进行了不对称的羟醛加成反应。非对映异构体形成非Evans粗加合物8a-h的非对映选择性为75:25至99：1。烯醇化物的面部选择性由立体异构的N（4）-甲基取代基指示。羟醛加合物8a容易通过酸水解裂解，得到（95％ee）的（2S，3S）-3-羟基-2-甲基-3-苯基丙酸（9）。