2-[(R)-Hydroxy-((4S,5S)-5-isopropyl-4-methyl-4,5-dihydro-isoxazol-3-yl)-methyl]-cyclohexanone

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑啉类
• 英文名称: 2-[(R)-Hydroxy-((4S,5S)-5-isopropyl-4-methyl-4,5-dihydro-isoxazol-3-yl)-methyl]-cyclohexanone
• 英文别名: 2-[(R)-hydroxy-[(4S,5S)-4-methyl-5-propan-2-yl-4,5-dihydro-1,2-oxazol-3-yl]methyl]cyclohexan-1-one
• 化学式: C₁₄H₂₃NO₃
• 分子量: 253.342
• InChiKey: NBRJTLREOGUSFE-GQIGNIDQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  58.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  顺式-4-甲基-2-戊烯 在 potassium hydrogensulfate 、 三氟化硼乙醚 、 水 、 silica gel 、 异氰酸苯酯 、 三乙胺 作用下， 以 四氯化碳 、 二氯甲烷 、 环戊烷 、 苯 为溶剂， 反应 30.0h， 生成 2-[(R)-Hydroxy-((4S,5S)-5-isopropyl-4-methyl-4,5-dihydro-isoxazol-3-yl)-methyl]-cyclohexanone
  参考文献：
  名称：

  Lewis acid promoted stereoselective carbon-carbon bond formation of 3-formyl-.DELTA.2-isoxazolines

  摘要：

  4,5-Disubstituted 3-formyl-DELTA2-isoxazolines undergo the aldol, allylation, and carbonyl ene reactions in the presence of appropriate Lewis acid to give the adducts with an effective 1,3-asymmetric induction. The stereoselectivity of the reaction mainly depends on the nature of the Lewis acid and the relative configuration of the ring. It is remarkable that both diastereomers can be readily prepared stereoselectively. For example, TiCl4 promotes the 1,3-syn-selective aldol reaction over 93/7 of selectivity, while the 1,3-anti adducts are prepared by the reaction catalyzed by BF3.OEt2. This difference in stereoselectivity is to be attributed to the preferable conformation of isoxazoline-Lewis acid complex intermediates, which depends on the nature of Lewis acid. Without the 4-substituent of isoxazolines the selectivity is not observed. The 5-substituent is too far from the formyl carbon to influence the face differentiation of the formyl group. Subsequent treatment of the adducts with LiAlH4 affords 2-amino 1,4-diol derivatives. The protective group of the hydroxyl group on the C(3) side chain is crucial for the stereoselectivity of the reduction. An almost complete diastereoselectivity of the relative configuration at four contiguous stereogenic centers is readily achieved by the reduction of the adducts protected by O-methoxymethyl (O-MOM). Consequently, the present strategy provides a facile method for the preparation of the compounds containing a sequence of several stereocenters.

  DOI：

  10.1021/jo00046a023

文献信息

• syn- and anti-Selective preparation of 3-substltuted-Δ2-isoxazolines
  作者：Akio Kamimura、Shinji Marumo

  DOI：10.1016/s0040-4039(00)97804-3

  日期：1990.1
• Lewis acid promoted stereoselective carbon-carbon bond formation of 3-formyl-.DELTA.2-isoxazolines
  作者：Akio Kamimura、Kosei Yoshihara、Shinji Marumo、Akinori Yamamoto、Takeshi Nishiguchi、Akikazu Kakehi、Kenzi Hori

  DOI：10.1021/jo00046a023

  日期：1992.9

  4,5-Disubstituted 3-formyl-DELTA2-isoxazolines undergo the aldol, allylation, and carbonyl ene reactions in the presence of appropriate Lewis acid to give the adducts with an effective 1,3-asymmetric induction. The stereoselectivity of the reaction mainly depends on the nature of the Lewis acid and the relative configuration of the ring. It is remarkable that both diastereomers can be readily prepared stereoselectively. For example, TiCl4 promotes the 1,3-syn-selective aldol reaction over 93/7 of selectivity, while the 1,3-anti adducts are prepared by the reaction catalyzed by BF3.OEt2. This difference in stereoselectivity is to be attributed to the preferable conformation of isoxazoline-Lewis acid complex intermediates, which depends on the nature of Lewis acid. Without the 4-substituent of isoxazolines the selectivity is not observed. The 5-substituent is too far from the formyl carbon to influence the face differentiation of the formyl group. Subsequent treatment of the adducts with LiAlH4 affords 2-amino 1,4-diol derivatives. The protective group of the hydroxyl group on the C(3) side chain is crucial for the stereoselectivity of the reduction. An almost complete diastereoselectivity of the relative configuration at four contiguous stereogenic centers is readily achieved by the reduction of the adducts protected by O-methoxymethyl (O-MOM). Consequently, the present strategy provides a facile method for the preparation of the compounds containing a sequence of several stereocenters.