(2'S,3'S,5S,6R)-3,4,5,6-tetrahydro-3-(3'-hydroxy-2'-methyl-3'-phenyl-propionyl)-4,5-dimethyl-6-phenyl-2H-1,3,4-oxadiazin-2-one | 476013-32-8

• 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: (2'S,3'S,5S,6R)-3,4,5,6-tetrahydro-3-(3'-hydroxy-2'-methyl-3'-phenyl-propionyl)-4,5-dimethyl-6-phenyl-2H-1,3,4-oxadiazin-2-one
• 英文别名: (2'S,3'S,5S,6R)-3,4,5,6-tetrahydro-3-(3-hydroxy-2-methyl-3-phenylpropionyl)-4,5-dimethyl-6-phenyl-1,3,4-oxadiazin-2-one；(5S,6R)-3-[(2S,3S)-3-hydroxy-2-methyl-3-phenylpropanoyl]-4,5-dimethyl-6-phenyl-1,3,4-oxadiazinan-2-one
• CAS: 476013-32-8
• 化学式: C₂₁H₂₄N₂O₄
• 分子量: 368.433
• InChiKey: YIUWAMOYWOGTJY-LNMJFAINSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  27
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  70.1
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2'S,3'S,5S,6R)-3,4,5,6-tetrahydro-3-(3'-hydroxy-2'-methyl-3'-phenyl-propionyl)-4,5-dimethyl-6-phenyl-2H-1,3,4-oxadiazin-2-one 在 硫酸 作用下， 以71%的产率得到(-)-(2S,3S)-3-hydroxy-2-methyl-3-phenylpropanoic acid
  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
• 作为产物：
  描述：

  麻黄碱 在 盐酸 、 lithium aluminium tetrahydride 、 四氯化钛 、 lithium hydride 、 三乙胺 、 sodium nitrite 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 4.0h， 生成 (2'S,3'S,5S,6R)-3,4,5,6-tetrahydro-3-(3'-hydroxy-2'-methyl-3'-phenyl-propionyl)-4,5-dimethyl-6-phenyl-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

• 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.
• Synthesis, X-ray crystallography and computational studies concerning an oxadiazinone derived from d-camphor: a structural limitation of oxadiazinones as chiral auxiliaries
  作者：Michael D. Squire、Ryan A. Davis、Karah A. Chianakas、Gregory M. Ferrence、Jean M. Standard、Shawn R. Hitchcock

  DOI：10.1016/j.tetasy.2005.01.020

  日期：2005.3

  A camphor-based oxadiazinone was prepared by reaction of the N-nitroimine of D-camphor with (1R,2S)-norephedrine; the reduction of the resultant imine; N-nitrosation of the amine; reduction to the corresponding hydrazine and cyclization. The conformational behaviour of oxadiazinone 7 was modeled in the gas and solution phases using the semiempirical AM1 method and density functional theory. Application of the oxadiazinone in the titanium mediated asymmetric aldol reaction provided the highly diastereoselective formation of the expected syn-adducts 8a-d as evidenced by single crystal X-ray diffraction analysis. Attempts to remove the oxadiazinone auxiliary using acidic or basic conditions failed to yield the expected beta-hydroxyacid in significant yield. (C) 2005 Elsevier 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）。