l-menthyl (2S)-2,6-dimethyl-4-oxo-1,3-dioxine-2-carboxylate | 167391-19-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: l-menthyl (2S)-2,6-dimethyl-4-oxo-1,3-dioxine-2-carboxylate
• CAS: 167391-19-7
• 化学式: C₁₇H₂₆O₅
• 分子量: 310.39
• InChiKey: DODMIMQNMKLGGP-WFTWPBCJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.18
• 重原子数：
  22.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.76
• 拓扑面积：
  61.83
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  l-menthyl (2S)-2,6-dimethyl-4-oxo-1,3-dioxine-2-carboxylate 在 palladium on activated charcoal 氢气 作用下， 以 乙酸乙酯 为溶剂， 45.0 ℃ 、7.09 MPa 条件下， 反应 72.0h， 生成 l-menthyl (2S,6R)-2,6-dimethyl-4-oxo-1,3-dioxane-2-carboxylate 、 l-menthyl (2S,6S)-2,6-dimethyl-4-oxo-1,3-dioxane-2-carboxylate
  参考文献：
  名称：

  Use of 1,3-Dioxin-4-ones and Related Compounds in Synthesis. 46. 2-(l-Menthyloxycarbonyl)-2,6-dimethyl-1,3-dioxin-4-one and Related Compounds. Relationship between Facial Selectivity and Pyramidalization

  摘要：

  Preparation and ground-state reactions (conjugate addition and catalytic hydrogenation) of a 1,3-dioxin-4-one having an l-menthyloxycarbonyl group at the 2-position as the only substituent (7a) and its 6-methyl derivative (8a), as well as their 2-methyl derivatives (5a and 6a), are reported. The X-ray structure of the 2(methoxycarbonyl)-2-phenyl derivative (4b) was also determined. The result, when combined with previously reported X-ray crystallographic analyses on related dioxinones, suggests that all of the dioxinones take, a sofa conformation of the six-membered ring, whose top face is always on the same side as the pyramidalization of the enone function in the ring, Conjugate addition reaction of 5a leads to exclusive addition on the bottom face, while addition to 7a gives the product corresponding to the top face addition, Catalytic hydrogenation of 6a and ga is also reported. Though the selectivity is much lowered as compared with the conjugate addition, the same facial selectivities are again observed. A comparison with the exclusive top face attack on 2-tert-butyl-1,3-dioxin-4-one (1) and its 2-methyl derivative 2 and bottom face attack on 2-(l-menthyloxycarbonyl)-2-phenyl-1,3-dioxin-4-one (3a) makes it clear that the prediction of facial selectivity in these ground-state reactions (conjugate addition and catalytic hydrogenation) based on pyramidalization is not always correct. A novel hypothesis which accounts for all of the above results (sofa conformation of the hetero ring, pyramidalization at the enone portion, and facial selectivity) is presented.

  DOI：

  10.1021/ja00120a009
• 作为产物：
  描述：

  2,2,6-三甲基-4H-1,3-二英-4-酮 在 4-二甲氨基吡啶 、 jones reagent 、 水 、 N,N'-二环己基碳二亚胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 丙酮 、 甲苯 为溶剂， 反应 47.5h， 生成 l-menthyl (2S)-2,6-dimethyl-4-oxo-1,3-dioxine-2-carboxylate
  参考文献：
  名称：

  Synthesis of optically active 1,3-dioxin-4-one derivatives having a hydroxymethyl group at the 2-position and their use for regio-, diastereo-, and enantioselective synthesis of substituted cyclobutanols

  摘要：

  A new method for preparing optically active 1,3-dioxin-4-one derivatives is presented. A series of prochiral 2,2-bis(hydroxymethyl)-1,3-dioxin-4-ones was synthesized by [4+2]cycloaddition of acylketene to protected 1,3-dihydroxy-2-propanone derivatives followed by deprotection of the hydroxyl groups. Desymmetrization of the prochiral dioxinones by lipase-catalyzed monoacetylation afforded optically active 2-(hydroxymethyl)dioxin ones. Intramolecular photo[2+2]cycloaddition of W-alkenyl esters of these alcohols provided an efficient method for regio-, diastereo-, and enantio selective synthesis of cyclobutanols. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00760-7