(4R,5R)-5-Isopropyl-4-methyl-4,5-dihydro-isoxazole-3-carbaldehyde | 131362-99-7

• 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: (4R,5R)-5-Isopropyl-4-methyl-4,5-dihydro-isoxazole-3-carbaldehyde
• 英文别名: (4R,5R)-4-methyl-5-propan-2-yl-4,5-dihydro-1,2-oxazole-3-carbaldehyde
• CAS: 131362-99-7
• 化学式: C₈H₁₃NO₂
• 分子量: 155.197
• InChiKey: MQBZWEYTIZLYFL-HTRCEHHLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.23
• 重原子数：
  11.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  38.66
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  1-环己烯氧基三甲基硅烷 、 (4R,5R)-5-Isopropyl-4-methyl-4,5-dihydro-isoxazole-3-carbaldehyde 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以89%的产率得到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
• 作为产物：
  描述：

  顺式-4-甲基-2-戊烯 在 potassium hydrogensulfate 、 水 、 silica gel 、 异氰酸苯酯 、 三乙胺 作用下， 以 四氯化碳 、 环戊烷 、 苯 为溶剂， 反应 28.0h， 生成 (4R,5R)-5-Isopropyl-4-methyl-4,5-dihydro-isoxazole-3-carbaldehyde
  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

• Diastereoselective Ene Reaction of 3-Formyl-Δ²-isoxazolines
  作者：Akio Kamimura、Akinori Yamamoto

  DOI：10.1246/cl.1990.1991

  日期：1990.11

  The ene reaction of 3-formyl-Δ2-isoxazolines proceeds smoothly in the presence of appropriate Lewis acid. An efficient 1,3-asymmetric induction takes place to give syn- and anti-homoallyl alcohols in a stereoselective way.

  三甲酰基Δ²-异恶唑啉的ene反应在适当的Lewis酸存在下顺利进行。在此过程中，高效地实现了1,3-不对称诱导，以立体选择性的方式得到了syn-和anti-同烯丙醇。
• Diastereoselective Cyclocondensation Reaction of 3-Formyl-2-isoxazolines
  作者：Akio Kamimura、Akikazu Kakehi

  DOI：10.1246/cl.1992.1133

  日期：1992.7

  The cyclocondensation reaction of 3-formyl-2-isoxazolines proceeds smoothly under the Lewis acid catalyzed conditions to give dihydropyran derivatives in moderate to high yields. Both diastereoisomers of the dihydropyrans, syn and anti, are prepared stereoselectively in the presence of an appropriate Lewis acid and solvent.

  3-甲酰基-2-异恶唑啉的环缩合反应在路易斯酸催化条件下顺利进行，以中等至高产率得到二氢吡喃衍生物。二氢吡喃的两种非对映异构体，顺式和反式，都是在适当的路易斯酸和溶剂存在下立体选择性地制备的。
• 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