Z-2-phenyl-4-<(S)-2,2-dimethyl-1,3-dioxolan-4-ylmethylen>-5(4H)-oxazolone | 154663-54-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: Z-2-phenyl-4-<(S)-2,2-dimethyl-1,3-dioxolan-4-ylmethylen>-5(4H)-oxazolone
• 英文别名: Z-2-Phenyl-4-[(S)-2,2-dimethyl-1,3-dioxolan-4-ylmethylen]-5(4H)-oxazolone；(4Z)-4-[[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]methylidene]-2-phenyl-1,3-oxazol-5-one
• CAS: 154663-54-4
• 化学式: C₁₅H₁₅NO₄
• 分子量: 273.288
• InChiKey: RYNZXKIYXZEHJB-LCFDYFRESA-N

物化性质

• 沸点：
  393.2±50.0 °C(Predicted)
• 密度：
  1.27±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  57.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Z-2-phenyl-4-<(S)-2,2-dimethyl-1,3-dioxolan-4-ylmethylen>-5(4H)-oxazolone 在 sodium methylate 、 sodium hydride 作用下， 以 乙醚 为溶剂， 反应 0.5h， 生成 methyl (1S,2R)-1-benzamido-2-<(S)-2,2-dimethyl-1,3-dioxolan-4-yl>cyclopropanecarboxylate
  参考文献：
  名称：

  手性恶唑酮与氧代砜亚砜环丙烷化反应的研究

  摘要：

  研究了由1,2-O-异亚丙基-D-甘油醛衍生的手性Z-恶唑酮对作为环丙烷化剂的亚砜基phon的行为。描述了产物比例对溶剂和温度的依赖性。

  DOI：

  10.1016/0040-4020(95)00033-5
• 作为产物：
  描述：

  马尿酸 、 双丙酮-D-甘露糖醇 在 lead(IV) acetate 、 乙酸酐 作用下， 生成 Z-2-phenyl-4-<(S)-2,2-dimethyl-1,3-dioxolan-4-ylmethylen>-5(4H)-oxazolone
  参考文献：
  名称：

  Study of the asymmetric diels-alder reaction of a chiral azlactone

  摘要：

  The chiral Z-azlactone derived from 1,2-O-isopropylidene-D-glyceraldehyde underwent diastereoselective Diels-Alder reaction with cyclopentadiene. Catalyst, temperature and solvent dependence of the product ratio is described.

  DOI：

  10.1016/0957-4166(94)80040-5

文献信息

• 1,3-Dipolar cycloaddition of diazomethane to chiral azlactones. Experimental and theoretical studies
  作者：Carlos Cativiela、María D. Díaz-de-Villegas、JoséI. García、Ana I. Jiménez

  DOI：10.1016/s0040-4020(97)00120-8

  日期：1997.3

  The reaction of (E)-2-phenyl-4-[(S)-2,2-dimethyl-1,3-dioxolan-4-ylmethylen]-5(4H)-oxazolone with diazomethane has been studied under a variety of reaction conditions, and the results compared with those obtained with the corresponding (Z)-isomer. The origin of the high diastereofacial selectivity in the cyclopropane products, observed with both oxazolones, is discussed in the light of theoretical calculations

  （E）-2-苯基-4-[（S）-2,2-二甲基-1,3-二氧戊环-4-基亚甲基] -5（4 H）-恶唑酮与重氮甲烷的反应已在多种条件下进行了研究反应条件，并将结果与​​用相应的（Z）-异构体获得的结果进行比较。根据第一步反应的理论计算，即在半经验（AM1）下进行的重氮甲烷的1,3-偶极环加成，讨论了用两种恶唑酮观察到的环丙烷产物中高非对映选择性的起源。）和从头算起（RHF / 3-21G）级别。两个理论水平正确预测在协同反应途径，导致所述的不对称诱导的方向Δ 1 -吡唑啉。AM1计算还预测了逐步反应路径的存在，该反应会导致开链反应中间体，但从头算结果并不支持。
• Z -2-Phenyl-4-[(S)- 2,2-dimethyl-1,3-dioxolan-4-ylmethylen]-5(4H)-oxazolone as the Dienophile in Asymmetric Diels-Alder Reactions
  作者：Elena Buñuel、Carlos Cativiela、Maria D. Diaz-de-Villegas

  DOI：10.1016/0040-4020(95)00501-x

  日期：1995.8

  Diels-Alder reactions of Z-2-phenyl-4-[(S)-2,2-dimethyl-1,3-dioxolan-4-ylmethylen]-5(4H)-oxazolone and several cyclic and open chain dienes are studied. Less-reactive dienes required longer reaction times and led to isomerization of the Z-oxazolone and isolation of products derived from the E-isomer; Lewis acid catalysts were used to shorten the reaction times. In all cases high diastereofacial selectivity

  研究了Z-2-苯基-4-[（S）-2,2-二甲基-1,3-二氧戊环-4-基亚甲基] -5（4H）-恶唑酮与几种环状和开链二烯的Diels-Alder反应。反应性较低的二烯需要更长的反应时间，并导致Z-恶唑酮的异构化和E异构体衍生产物的分离；使用路易斯酸催化剂来缩短反应时间。在所有情况下，均观察到高非对映体选择性，并且可以以高光学纯度获得Diels-Alder加合物。加合物的立体化学已通过单晶X射线结构测定，1 H-NMR分析和机理考虑得到阐明。
• A simple synthesis of (−)-(1S,2R)-allocoronamic acid in its enantiomerically pure form
  作者：Carlos Cativiela、María D. Díaz-de-Villegas、Ana I. Jiménez

  DOI：10.1016/0957-4166(94)00373-j

  日期：1995.1

  (−)-(1S,2R)-Allocoronamic acid was synthesized in its enantiomerically pure form by starting from the chiral azlactone derived from 1,2-O-isopropylidene-D-glyceraldehyde in an overall yield of 37 %.

  通过从衍生自1,2-O-异亚丙基-D-甘油醛的手性氮杂内酯为原料，以对映体纯的形式合成（-）-（1S，2R）-别香醛酸，总产率为37％。
• 1,3-Dipolar cycloaddition of diazomethane with a chiral azlactone
  作者：Carlos Cativiela、María D Díaz-de-Villegas、Ana I Jiménez、Fernando Lahoz

  DOI：10.1016/s0040-4039(00)75853-9

  日期：1994.1

  The chiral Z-azlactone derived from 1,2-O-isopropylidene-D-glyceraldehyde reacted with diazomethane to afford stereoselectively and diastereoselectively a cis spiro-azlactone. Solvent and temperature dependence of the ratio of the products is described
• Atmospheric pressure chemical ionization multi-stage mass spectrometry in the characterization of stereoisomeric synthons of cyclopropane amino acids
  作者：Simone Cristoni、Carlos Cativiela、Ana I. Jim�nez、Pietro Traldi

  DOI：10.1002/(sici)1096-9888(200002)35:2<199::aid-jms930>3.0.co;2-6

  日期：2000.2

  The mass spectrometric behaviour of (1S,2R)-, (1R,2R)-, (1R,2S)- and (1S,2S)-2-[(S)-2,2-dimethyl-1, 3-dioxolan-4-yl]-1-spiro-¿4'[2'-phenyl-5'(4'H)-oxazolone]¿ cyclopropane (2) and (1S,2R)-, (1R,2R)-, (1R,2S)- and (1S, 2S)-methyl-1-benzamido-2-[(S)-2,2-dimethyl-1, 3-dioxolan-4-yl]cyclopropanecarboxylate (3) was studied under atmospheric pressure ionization conditions and by multi-stage mass spectrometric (MS(n)) experiments performed with an ion trap. Interestingly, by using methanol as solvent, compounds 2 lead to [M + H + CH(3)OH](+) ions which, as proved by collisional experiments, exhibit the same structure of the corresponding compound 3. MS/MS of [MH](+) ions allows a clear characterization of the different stereoisomers, which give rise to specific fragmentation pathways, rationalized with respect to the structure of the neutral molecules.