(5S,6R)-4,5-dimethyl-6-phenyl-3,4,5,6-tetrahydro-2H-1,3,4-oxadiazin-2-one | 397332-61-5

• 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-3,4,5,6-tetrahydro-2H-1,3,4-oxadiazin-2-one
• 英文别名: (5S,6R)-4,5-dimethyl-6-phenyl-1,3,4-oxadiazinan-2-one；cis-(-)-4,5-Dimethyl-6-phenyl-2-oxo-3,4,5,6-tetrahydro-2H-1,3,4-oxadiazin；(5S)-4,5r-dimethyl-6c-phenyl-[1,3,4]oxadiazinan-2-one
• CAS: 397332-61-5
• 化学式: C₁₁H₁₄N₂O₂
• 分子量: 206.244
• InChiKey: UXVSYSJHNUGVCD-WPRPVWTQSA-N

物化性质

• 密度：
  1.113±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  41.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (5S,6R)-4,5-dimethyl-6-phenyl-3,4,5,6-tetrahydro-2H-1,3,4-oxadiazin-2-one 在 四氯化钛 、 lithium hydride 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 4.0h， 生成 (2'S,3'S,5S,6R)-3-[3'-(1,3-dihydro-isobenzofuran-5-yl)-3'-hydroxy-2'-methyl-propionyl]-3,4,5,6-tetrahydro-4,5-dimethyl-6-phenyl-2H-1,3,4-oxadiazinan-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
• 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 为溶剂， 生成 (5S,6R)-4,5-dimethyl-6-phenyl-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

• Formation of Complex Hydrazine Derivatives via Aza-Lossen Rearrangement
  作者：Dilan E. Polat、David D. Brzezinski、André M. Beauchemin

  DOI：10.1021/acs.orglett.9b01742

  日期：2019.6.21

  The development of a broadly applicable procedure for the aza-Lossen rearrangement is reported. This process converts amines into complex hydrazine derivatives in two steps under safe, mild conditions. This method allows the chemoselective formation of N–N bonds, resulting in the synthesis of cyclic and acyclic products while avoiding side reactions of the amphoteric (ambident) nitrogen-substituted

  据报道开发了可广泛用于氮杂-洛森重排的程序。此过程可在安全，温和的条件下分两步将胺转化为复杂的肼衍生物。该方法允许化学选择性地形成N–N键，从而合成环状和非环状产物，同时避免了两性（环境性）氮取代的异氰酸酯中间体的副反应。
• Asymmetric conjugate addition reactions with chiral oxadiazinones: Unusual conformational properties of the oxadiazinones
  作者：Fatima Olayemi Obe、Ryan A. Davis、Jennifer Spurlock、Morgan M. Grunloh Barnes、Tyler Lindvall、Micah S. Wendorf、Christina Delach、Gregory M. Ferrence、Jean M. Standard、Shawn R. Hitchcock

  DOI：10.1016/j.tet.2021.132002

  日期：2021.3

  acylated, and examined in the asymmetric conjugate addition reaction with Grignard reagents in the presence of copper(I) bromide-dimethyl sulfide complex. The highest diastereoselectivity that was obtained in the conjugate addition reaction was observed with the (1R,2S)-ephedrine based N4-methyloxadiazinone (5:1 d.r.) favoring the formation of the (S)-configuration of the conjugate addition product. Efforts

  在溴化铜（I）-二甲基硫醚络合物的存在下，已制备了一系列基于麻黄的氧二嗪酮，将其酰化并在与格氏试剂的不对称共轭加成反应中进行了研究。在基于（1 R，2 S）-麻黄碱的N 4-甲基恶二嗪酮（5：1 dr）中观察到在共轭加成反应中获得的最高非对映选择性，这有利于共轭加成产物的（S）-构型的形成。。通过增加恶二嗪酮的立体定向N 4-取代基的空间体积来增加非选择性的水平的努力（N 4- =  p-甲氧基苯基或-异丙基）导致非对映选择性水平的降低。的计算研究以检查通过的构象Ñ 4 -methyloxadiazinone与所述Ñ 4 -异丙基- oxadiazinone即，产生非对映选择性较低。对于N 4-取代基的立体电子性质是适度的非对映选择性和共轭加成的出乎意料的面部偏爱的原因，存在争论。
• 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。
• Towards the development of oxadiazinanones as chiral auxiliaries: synthesis and application of N3-haloacetyloxadiazinanones
  作者：Trisha R. Hoover、Jonathan A. Groeper、Raleigh W. Parrott、Seshanand P. Chandrashekar、Jennifer M. Finefield、Alexandro Dominguez、Shawn R. Hitchcock

  DOI：10.1016/j.tetasy.2006.06.036

  日期：2006.7

  Oxadiazinanones derived from (1R,2S)-ephedrine and (1R,2S)-norephedrine were employed in the asymmetric alpha-halo aldol reaction. The optimized yields and diastereoselectivities for the ephedrine based oxadiazinanone aldol reaction ranged from fair to good. The ephedrine based aldol adducts were hydrolyzed to afford the alpha-bromo-beta-hydroxycarboxylic acids. The absolute stereochemistry and enantiomeric purity of these products were determined by chiral HPLC and specific rotation measurements. (c) 2006 Elsevier Ltd. All rights reserved.
• 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.