methyl (1R,6R)-1-benzamido-6-<(S)-2,2-dimethyl-1,3-dioxolan-4-yl>-4-oxo-2-cyclohexen-1-carboxylate | 174506-58-2

• 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 (1R,6R)-1-benzamido-6-<(S)-2,2-dimethyl-1,3-dioxolan-4-yl>-4-oxo-2-cyclohexen-1-carboxylate
• 英文别名: methyl (1R,6R)-1-benzamido-6-<(4S)-4-(2,2-dimethyl-1,3-dioxolo)>-4-oxo-2-cyclohexen-1-carboxylate；methyl (1S,6R)-1-benzamido-6-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-4-oxocyclohex-2-ene-1-carboxylate
• CAS: 174506-58-2
• 化学式: C₂₀H₂₃NO₆
• 分子量: 373.406
• InChiKey: RSGKYZILRAUTIN-YRNRMSPPSA-N

物化性质

• 沸点：
  562.9±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)：
  1.5
• 重原子数：
  27
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 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 (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 、 potassium tri-sec-butyl-borohydride 作用下， 以 四氢呋喃 、 乙酸乙酯 为溶剂， 反应 1.0h， 生成 methyl (1S,2R,4R)-1-benzamido-2-[(S)-2,2-dimethyl-1,3-dioxolan-4-yl]-4-hydroxycyclohexane-1-carboxylate
  参考文献：
  名称：

  以（R）-甘油醛为原料的手性不饱和恶唑酮通过Diels-Alder反应合成脯氨酸

  摘要：

  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。

  DOI：

  10.1016/s0040-4020(01)00533-6
• 作为产物：
  描述：

  (1S,2S,6R)-6-<(S)-2,2-dimethyl-1,3-dioxolan-4-yl>-2-methoxy-4-oxo-cyclohexan-1-spiro<4'<2'-phenyl-5'(4'H)-oxazolone>> 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 10.0h， 以80%的产率得到methyl (1R,6R)-1-benzamido-6-<(S)-2,2-dimethyl-1,3-dioxolan-4-yl>-4-oxo-2-cyclohexen-1-carboxylate
  参考文献：
  名称：

  High-pressure and thermally induced asymmetric diels-alder cycloadditions of heterosubstituted dienes to homochiral α,β-didehydro amino acid derivatives

  摘要：

  An amino pentenoate and an unsaturated oxazolone have shown to be suitable homochiral dienophiles to be reacted with electron-rich heterosubstituted dienes. High-pressure and thermal activation have been studied for these cycloadditions. The adducts obtained are polyfunctional building blocks useful for the synthesis of enantiopure cyclohexane amino acids and related products.

  DOI：

  10.1016/0957-4166(95)00429-7

文献信息

• 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。
• [2 + 2]-Photocycloaddition of 1,1-Diethoxyethylene to Chiral Polyfunctional 2-Cyclohexenones. Regioselectivity and π-Facial Discrimination
  作者：Elena García-Expósito、Ángel Álvarez-Larena、Vicenç Branchadell、Rosa M. Ortuño

  DOI：10.1021/jo035532n

  日期：2004.2.1

  The photochemical [2 + 2]-cycloadditions of 1,1-diethoxyethylene to chiral polyfunctional 2-cyclo-hexenones have been carried out leading to the production of highly constrained unusual alpha-amino acids with excellent regioselectivity and satisfactory yields. Theoretical calculations have been done to rationalize the observed regio- and diastereoselectivity and show that regiochemistry is determined by the relative rate of formation of the 1,4-biradical intermediates and not by the stability of these species.
• 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
• High-pressure and thermally induced asymmetric diels-alder cycloadditions of heterosubstituted dienes to homochiral α,β-didehydro amino acid derivatives
  作者：Rosa M. Ortuño、Javier Ibarzo、Jean d'Angelo、Françoise Dumas、Angel Alvarez-Larena、Joan F. Piniella

  DOI：10.1016/0957-4166(95)00429-7

  日期：1996.1

  An amino pentenoate and an unsaturated oxazolone have shown to be suitable homochiral dienophiles to be reacted with electron-rich heterosubstituted dienes. High-pressure and thermal activation have been studied for these cycloadditions. The adducts obtained are polyfunctional building blocks useful for the synthesis of enantiopure cyclohexane amino acids and related products.
• 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。