(E,2R,6R)-2-tert-Butyl-5-ethyliden-6-methyl-1,3-dioxan-4-on | 129287-44-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 英文名称: (E,2R,6R)-2-tert-Butyl-5-ethyliden-6-methyl-1,3-dioxan-4-on
• 英文别名: (2R,5E,6R)-2-tert-butyl-5-ethylidene-6-methyl-1,3-dioxan-4-one
• CAS: 129287-44-1
• 化学式: C₁₁H₁₈O₃
• 分子量: 198.262
• InChiKey: APDRCOWRJUJNIJ-QMCCYZMISA-N

物化性质

• 沸点：
  309.3±42.0 °C(Predicted)
• 密度：
  1.051±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E,2R,6R)-2-tert-Butyl-5-ethyliden-6-methyl-1,3-dioxan-4-on 在 盐酸 作用下， 以 四氢呋喃 为溶剂， 反应 72.0h， 以92%的产率得到(E,3R)-2-Ethyliden-3-hydroxybutansaeure
  参考文献：
  名称：

  Amberg, Willi; Seebach, Dieter, Chemische Berichte, 1990, vol. 123, # 12, p. 2413 - 2428

  摘要：

  DOI：
• 作为产物：
  描述：

  (2R,5R,6R)-2-tert-Butyl-5-(1-hydroxy-ethyl)-6-methyl-[1,3]dioxan-4-one 在 吡啶 、 4-二甲氨基吡啶 、 三乙胺 作用下， 以 氯仿 为溶剂， 反应 24.5h， 生成 (E,2R,6R)-2-tert-Butyl-5-ethyliden-6-methyl-1,3-dioxan-4-on
  参考文献：
  名称：

  Amberg, Willi; Seebach, Dieter, Chemische Berichte, 1990, vol. 123, # 12, p. 2413 - 2428

  摘要：

  DOI：

文献信息

• Optically active 1,5-benzothiazepin-4-ones by ring transformation of 5-ylidene-1,3-dioxan-4-ones with 2-aminothiophenol
  作者：Akbar Ali、Viqar Uddin Ahmad、Joachim Leistner、Jürgen Liebscher

  DOI：10.1039/b001928n

  日期：——

  Optically active cis- and trans-3-(1-hydroxyethyl)-1,5-benzothiazepin-4-ones 4 and 5 have been synthesised by ring transformation of (E)- and (Z)-5-ylidene-1,3-dioxan-4-ones 1 with 2-aminothiophenol. Stereoselective conjugate addition of the –SH group of 2-aminothiophenol to the Michael system of the chiral 5-ylidene-1,3-dioxan-4-one 1, catalysed by BuLi, gave adducts 2 and 3. The stereochemical mode of attack can be rationalised by hydrogen bonding of the attacking 2-aminothiophenolate with the oxygen atoms of the dioxanone ring. Treatment of the adducts 2 and 3 with ethylmagnesium bromide afforded ring transformation by attack of the amino group at the carbonyl carbon atom cleaving the dioxanone ring. The resulting 3-(1-hydroxyethyl)-1,5-benzothiazepin-4-ones 4 and 5 represent structural analogues of Diltiazem®, a widely used drug in the treatment of hypertension.

  通过(E)-和(Z)-5-亚基-1,3-二氧杂环-4-酮 1 与 2-氨基苯硫酚的环转化，合成了具有光学活性的顺式和反式-3-(1-羟乙基)-1,5-苯并硫氮杂卓-4-酮 4 和 5。在 BuLi 催化下，2-氨基苯硫酚的 -SH 基团与手性 5-亚基-1,3-二氧杂环-4-酮 1 的迈克尔体系进行立体选择性共轭加成，得到加合物 2 和 3。2- 氨基噻吩酚与二噁烷酮环上的氧原子发生氢键反应，从而合理地解释了反应的立体化学模式。用溴化乙锭处理加合物 2 和 3，通过氨基攻击羰基碳原子裂解二噁烷酮环，实现环转化。由此产生的 3-（1-羟乙基）-1,5-苯并硫氮杂卓-4-酮 4 和 5 代表了地尔硫卓® 的结构类似物，地尔硫卓® 是一种广泛用于治疗高血压的药物。
• Stereoselective synthesis of 3,4-disubstituted pyroglutamates by ring transformation of 5-ylidene-1,3-dioxan-4-ones with N-(diphenylmethylene)-glycinate
  作者：Akbar Ali、Viqar Uddin Ahmad、Burkhard Ziemer、Jürgen Liebscher

  DOI：10.1016/s0957-4166(00)00403-1

  日期：2000.11

  N-(Diphenylmethylene)-glycinate gives stereoselective conjugate addition to readily available (E) and (Z)-5-ylidene-1,3-dioxan-4-ones. Hydrolytic cleavage of the imine functionality of the resulting Michael-adducts causes ring transformation to new, optically active 3,4-disubstituted pyroglutamates. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Stereoselective Synthesis of Thiochroman-4-ones by Ring Transformation of Chiral 5-Ylidene-1,3-dioxan-4-ones with 2-Bromothiophenol via Bromo−Lithium Exchange
  作者：Akbar Ali、Viqar Uddin Ahmad、Jürgen Liebscher

  DOI：10.1002/1099-0690(200102)2001:3<529::aid-ejoc529>3.0.co;2-b

  日期：2001.2

  The reaction of (E)- or (Z)-5-ylidene-1,3-dioxan-4-one (1) and 2-bromothiophenol, followed by bromo-lithium exchange with nBuLi, provides a new access to optically active thiochroman-4-ones 4 and 5. Stereoselective conjugate addition occurs in the first step and the resulting 5-(1-phenylsulfanylalkyl)-1,3-dioxan-4-ones 2 and 3 undergo ring transformation to thiochroman-4-ones by attack of the lithiated phenyl ring at the dioxanone carbonyl carbon atom, cleaving off pivalaldehyde. If reactants with a (Z)-configuration are used, a retro-aldol reaction occurs in the ring transformation step, thus affording the 3-unsubstituted thiochroman-4-ones 5 rather than 3-(l-hydroxyethyl)-thiochroman-4-ones 4. This phenomenon can be rationalized by the steric congestion in the intermediate enolate 7.
• Stereoselective Diazoalkane Cycloadditions to Chiral 5-Alkylidene-1,3-dioxan-4-ones and 3-Benzylidene-β-lactones
  作者：Annett Bartels、Peter G. Jones、Jürgen Liebscher

  DOI：10.1055/s-1998-2195

  日期：1998.11
• Enantioselective synthesis of hydroxyethyloxiranecarboxylic acid derivatives by epoxidation of 5-ylidene-1,3-dioxane-4-ones
  作者：Annett Bartelts、Peter G. Jones、Jürgen Liebscher

  DOI：10.1016/0957-4166(95)00193-s

  日期：1995.7

  Epoxidation of the 5-ylidene-1,3-dioxane-4-ones 3 with dimethyldioxirane (4) affords enantiomerically pure oxiranes 5 in satisfactory yields. These products 5 are novel hydroxyethyloxiranecarboxylic acid derivatives and can be reduced to enantiomerically pure 5-(alpha-hydroxyalkyl)- 1,3-dioxane-4-ones 6.