(3R*,5S*)-2,5-dimethyl-3,5-diphenylisoxazolidine | 110317-60-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: (3R*,5S*)-2,5-dimethyl-3,5-diphenylisoxazolidine
• 英文别名: (+/-)-cis-2,5-dimethyl-3,5-diphenylisoxazolidine；(3R,5S)-2,5-dimethyl-3,5-diphenyl-1,2-oxazolidine
• CAS: 110317-60-7
• 化学式: C₁₇H₁₉NO
• 分子量: 253.344
• InChiKey: PKNIPRFWOASSTK-SJORKVTESA-N

物化性质

• 沸点：
  358.3±52.0 °C(Predicted)
• 密度：
  1.066±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3R*,5S*)-2,5-dimethyl-3,5-diphenylisoxazolidine 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 7.5h， 生成 (3E)-2,4-diphenylbut-3-en-2-ol
  参考文献：
  名称：

  Ring-opening of Isoxazolidine Nucleus by Trimethyl Posphate Treatment: Formation of Tertiary Allylic Alcohols via Intermediate 1,3-Oxazinium Salts

  摘要：

  5,5-Disubstituted isoxazolidines undergo ring opening reaction, leading to tertiary allylic alcohols, by sequential treatment with trimethyl phosphate (TMP) and NaH. The reaction proceeds through sequence steps which involve an initial alkylation to isoxazolidinium intermediate, followed by ring expansion to tetrahydro-1,3-oxazine, further alkylation and a Hofmann-like elimination towards the final products promoted by NaH.

  DOI：

  10.3987/com-92-6239
• 作为产物：
  描述：

  N-methyl-α-phenylnitrone 、 2-苯基-1-丙烯 以 甲苯 为溶剂， 反应 51.0h， 以23%的产率得到(3R*,5S*)-2,5-dimethyl-3,5-diphenylisoxazolidine
  参考文献：
  名称：

  Kinetic Resolution of Isoxazolidines by a Pd−BINAP Complex

  摘要：

  Asymmetric decomposition of isoxazolidine derivatives under catalysis by optically active palladium(ii) complexes was examined. When racemic ethyl cis-2,5-dimethyl-5-phenylisoxazolidine-3-carboxylate (cis-1a) was treated with a catalytic amount of [Pd(MeCN)(2){(S)-TolBINAP}](BF4)2 in CH2Cl2 for 60 h, optically active substrate was recovered with 99% ee and in 48% yield. The highest selectivity was achieved on treatment of racemic ethyl trans-2,4-dimethyl-5,5-diphenylisoxazolidine-3-carboxylate, to give the optically active substrate in 74% yield with 35% ee. The k(f)/k(s) value of this reaction reaches as high as 732. For this decomposition, each substrate should have both a methyl group on the 2-position and an alkoxycarbonyl group on the 3-position of the isoxazolidine ring. The enantioselectivities of the recovered substrates were influenced not only by the other substituent groups on the 4- and 5-positions but also by the geometrical structures of the substrates.

  DOI：

  10.1002/1099-0690(200211)2002:22<3855::aid-ejoc3855>3.0.co;2-4

文献信息

• Liguori, Angelo; Romeo, Giovanni; Sindona, Giovanni, Chemische Berichte, 1988, vol. 121, p. 105 - 110
  作者：Liguori, Angelo、Romeo, Giovanni、Sindona, Giovanni、Uccella, Nicola

  DOI：——

  日期：——
• Ring-opening of Isoxazolidine Nucleus by Trimethyl Posphate Treatment: Formation of Tertiary Allylic Alcohols via Intermediate 1,3-Oxazinium Salts
  作者：Ugo Chiacchio、Angelo Liguori、Giovanni Romeo、Giovanni Sindona、Nicola Uccella

  DOI：10.3987/com-92-6239

  日期：——

  5,5-Disubstituted isoxazolidines undergo ring opening reaction, leading to tertiary allylic alcohols, by sequential treatment with trimethyl phosphate (TMP) and NaH. The reaction proceeds through sequence steps which involve an initial alkylation to isoxazolidinium intermediate, followed by ring expansion to tetrahydro-1,3-oxazine, further alkylation and a Hofmann-like elimination towards the final products promoted by NaH.
• Kinetic Resolution of Isoxazolidines by a Pd−BINAP Complex
  作者：Tetsuo Ohta、Hiroyuki Kamizono、Aya Kawamoto、Kazushige Hori、Isao Furukawa

  DOI：10.1002/1099-0690(200211)2002:22<3855::aid-ejoc3855>3.0.co;2-4

  日期：2002.11

  Asymmetric decomposition of isoxazolidine derivatives under catalysis by optically active palladium(ii) complexes was examined. When racemic ethyl cis-2,5-dimethyl-5-phenylisoxazolidine-3-carboxylate (cis-1a) was treated with a catalytic amount of [Pd(MeCN)(2)(S)-TolBINAP}](BF4)2 in CH2Cl2 for 60 h, optically active substrate was recovered with 99% ee and in 48% yield. The highest selectivity was achieved on treatment of racemic ethyl trans-2,4-dimethyl-5,5-diphenylisoxazolidine-3-carboxylate, to give the optically active substrate in 74% yield with 35% ee. The k(f)/k(s) value of this reaction reaches as high as 732. For this decomposition, each substrate should have both a methyl group on the 2-position and an alkoxycarbonyl group on the 3-position of the isoxazolidine ring. The enantioselectivities of the recovered substrates were influenced not only by the other substituent groups on the 4- and 5-positions but also by the geometrical structures of the substrates.