methyl (1S,2R)-1-benzoylamino-2-[(4'S)-4'-(2',2'-dimethyl-1',3'-dioxolo)]-4-oxocyclohexane-1-carboxylate | 178976-47-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl (1S,2R)-1-benzoylamino-2-[(4'S)-4'-(2',2'-dimethyl-1',3'-dioxolo)]-4-oxocyclohexane-1-carboxylate
• 英文别名: methyl (1S,2R)-1-benzamido-2-[(S)-2,2-dimethyl-1,3-dioxolan-4-yl]-4-oxocyclohexane-1-carboxylate；methyl (1S,2R)-1-benzamido-2-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-4-oxocyclohexane-1-carboxylate
• CAS: 178976-47-1
• 化学式: C₂₀H₂₅NO₆
• 分子量: 375.422
• InChiKey: FMKOHDAYEIUXJM-YRNRMSPPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  27
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  90.9
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl (1S,2R)-1-benzoylamino-2-[(4'S)-4'-(2',2'-dimethyl-1',3'-dioxolo)]-4-oxocyclohexane-1-carboxylate 在 盐酸 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以84%的产率得到(1S,2R)-1-Benzoylamino-2-((S)-1,2-dihydroxy-ethyl)-4-oxo-cyclohexanecarboxylic acid methyl ester
  参考文献：
  名称：

  Z-2-phenyl-4-[(S)-2,2-dimethyl-1,3-dioxolan-4-ylmethylen]-5(4H)-oxazolone as the dienophile in asymmetric diels-alder reactions. II

  摘要：

  Diels-Alder reaction of Z-2-phenyl-4-[(S)-2,2-dimethyl-1,3-dioxolan -4-ylmethylen]-5(4H)-oxazolone and Danishefsky's diene is studied. Thermally induced reaction took place at room temperature with a high diastereofacial selectivity and Diels-Alder adducts, obtained in very high diastereomeric purity, were easily transformed into valuable compounds. The stereochemistry of the adducts has been elucidated by single crystal X-ray structure determinations, H-1-NMR analysis and mechanistic considerations. Copyright (C) 1996 Elsevier Science Ltd

  DOI：

  10.1016/0957-4166(96)00160-7
• 作为产物：
  描述：

  methyl (1R,6R)-1-benzamido-6-<(S)-2,2-dimethyl-1,3-dioxolan-4-yl>-4-oxo-2-cyclohexen-1-carboxylate 在 palladium on activated charcoal 氢气 作用下， 以 甲醇 为溶剂， 以100%的产率得到methyl (1S,2R)-1-benzoylamino-2-[(4'S)-4'-(2',2'-dimethyl-1',3'-dioxolo)]-4-oxocyclohexane-1-carboxylate
  参考文献：
  名称：

  立体选择性合成手性多官能化环己烷衍生物。钯（II）介导的环己酮与重氮甲烷之间的反应

  摘要：

  通过Diels-Alder环加成反应已经合成了几种手性多官能化环己酮和环己酮，X射线结构分析和NOE实验表明了立体选择性。研究了环己酮和重氮甲烷在钯（II）催化反应中的化学选择性。因此，在那些在γ-碳上具有酰胺功能的烯酮中，优先加成发生在羰基上，得到环氧化物，在酸性条件下，该环氧化物重排成四氢苯并恶唑。由于加成CnonC键，其他环己烯酮可提供环丙烷。提出了一种机械方法来解释整个过程。

  DOI：

  10.1016/s0040-4020(00)01061-9

文献信息

• Synthesis of constrained prolines by Diels–Alder reaction using a chiral unsaturated oxazolone derived from (R)-glyceraldehyde as starting material
  作者：Elena Buñuel、Ana M Gil、Marı́a D Dı́az-de-Villegas、Carlos Cativiela

  DOI：10.1016/s0040-4020(01)00533-6

  日期：2001.7

  This report describes a new route for the asymmetric synthesis of enantiomerically pure 2-substituted 7-azabicyclo[2.2.1]heptane-1-carboxylic acids, which are new conformationally constrained β-functionalised proline analogues. Our strategy is based on the preparation of a valuable azabicyclic intermediate by a key step that involves the intramolecular cyclisation of a derivative obtained from the

  该报告描述了对映体纯的2-取代的7-氮杂双环[2.2.1]庚烷-1-羧酸的不对称合成的新途径，所述新的构象受限的β-官能化的脯氨酸类似物。我们的策略是通过关键步骤制备有价值的氮杂双环中间体，该关键步骤涉及分子内环化衍生自衍生自（R）-甘油醛的手性恶唑酮的不对称Diels-Alder反应提供的加合物转化衍生的衍生物。与Danishefsky的二烯。该方法在（1 S，2 R，4 R）-7-氮杂双环[2.2.1]庚烷-1,2-二羧酸和（1 S，2 R，4 ）的合成中的应用R）-2-丙基-7-氮杂双环[2.2.1]庚烷-1-羧酸盐酸盐，也可以分别视为1-天冬氨酸和1-正亮氨酸类似物，可用于说明我们方法学的多功能性。
• Z-2-phenyl-4-[(S)-2,2-dimethyl-1,3-dioxolan-4-ylmethylen]-5(4H)-oxazolone as the dienophile in asymmetric diels-alder reactions. II
  作者：Elena Buñuel、Carlos Cativiela、Maria D Diaz-de-Villegas

  DOI：10.1016/0957-4166(96)00160-7

  日期：1996.5

  Diels-Alder reaction of Z-2-phenyl-4-[(S)-2,2-dimethyl-1,3-dioxolan -4-ylmethylen]-5(4H)-oxazolone and Danishefsky's diene is studied. Thermally induced reaction took place at room temperature with a high diastereofacial selectivity and Diels-Alder adducts, obtained in very high diastereomeric purity, were easily transformed into valuable compounds. The stereochemistry of the adducts has been elucidated by single crystal X-ray structure determinations, H-1-NMR analysis and mechanistic considerations. Copyright (C) 1996 Elsevier Science Ltd
• Stereoselective synthesis of chiral polyfunctionalized cyclohexane derivatives. Palladium(II)-mediated reaction between cyclohexenones and diazomethane
  作者：Cristóbal Rodrı́guez-Garcı́a、Javier Ibarzo、Ángel Álvarez-Larena、Vicenç Branchadell、Antoni Oliva、Rosa M Ortuño

  DOI：10.1016/s0040-4020(00)01061-9

  日期：2001.2

  been synthesized through Diels–Alder cycloadditions, stereoselectivity being stated by X-ray structural analysis and NOE experiments. The chemoselectivity in the palladium(II)-catalyzed reaction between cyclohexenones and diazomethane has been investigated. Thus, in those enones bearing an amide function on the γ-carbon, the preferential addition occurs at the carbonyl giving epoxides which, under acid

  通过Diels-Alder环加成反应已经合成了几种手性多官能化环己酮和环己酮，X射线结构分析和NOE实验表明了立体选择性。研究了环己酮和重氮甲烷在钯（II）催化反应中的化学选择性。因此，在那些在γ-碳上具有酰胺功能的烯酮中，优先加成发生在羰基上，得到环氧化物，在酸性条件下，该环氧化物重排成四氢苯并恶唑。由于加成CnonC键，其他环己烯酮可提供环丙烷。提出了一种机械方法来解释整个过程。