1-benzoyl-2(S)-tert-butyl-6(S)-carboxy-perhydropyrimidin-4-one | 143870-65-9

• 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: 1-benzoyl-2(S)-tert-butyl-6(S)-carboxy-perhydropyrimidin-4-one
• 英文别名: 1-benzoyl-(2S)-tert-butyl-(6S)-carboxyperhydropyrimidin-4-one；1-benzoyl-2(S)-tert-butyl-6(S)-carboxyperhydropyrimidin-4-one；(2S,4S)-3-Benzoyl-2-tert-butyl-6-oxohexahydro-4-pyrimidinecarboxylic acid；(2S,4S)-3-benzoyl-2-tert-butyl-6-oxo-1,3-diazinane-4-carboxylic acid
• CAS: 143870-65-9
• 化学式: C₁₆H₂₀N₂O₄
• 分子量: 304.346
• InChiKey: KFUQHFPYHCKQQQ-NHYWBVRUSA-N

物化性质

• 熔点：
  202-203 °C
• 沸点：
  566.9±50.0 °C(Predicted)
• 密度：
  1.239±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  86.7
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-benzoyl-2(S)-tert-butyl-6(S)-carboxy-perhydropyrimidin-4-one 在 palladium on activated charcoal lead(IV) acetate 、 正丁基锂 、 copper diacetate 、 氢气 、 溶剂黄146 作用下， 以 乙酸乙酯 为溶剂， -78.0~90.0 ℃ 、7.6 MPa 条件下， 反应 48.0h， 生成 1-benzoyl-2(S)-tert-butyl-3-methylperhydropyrimidin-4-one
  参考文献：
  名称：

  β-氨基酸的对映选择性合成。7.由1-苯甲酰基-2（S）-叔丁基-3-甲基全氢嘧啶-4-酮的对映体纯α-取代的β-氨基酸的制备。1,2

  摘要：

  廉价的天然α-氨基酸L-天冬酰胺被有效地转化为对映体纯态的（R）-或（S）-α-烷基化的β-氨基酸。该方案中的关键中间体是对映体N，N-乙缩醛嘧啶酮（S）-1 ，一种掩盖的β-丙氨酸手性衍生物。

  DOI：

  10.1016/0957-4166(96)00278-9
• 作为产物：
  描述：

  特戊醛 在 氢氧化钾 、 碳酸氢钠 作用下， 生成 1-benzoyl-2(S)-tert-butyl-6(S)-carboxy-perhydropyrimidin-4-one
  参考文献：
  名称：

  Preparation and assignment of configuration of 1-benzoyl- (2S)-tert-butyl-3-methyl-perhydropyrimidin-4-one. Useful starting material for the enantioselective synthesis of α-substituted β-amino acids

  摘要：

  (S) -Asparagine, an inexpensive beta-amino acid was converted into the title heterocycle (+)-1 in very good overall yield. The highly selective trans methylation of (+)-1-Li, and the hydrolysis of the resulting adduct afforded (R)-alpha-methyl-beta-alanine, allowing the assignment of the (S) configuration in (+)-1.

  DOI：

  10.1016/s0957-4166(00)80511-x

文献信息

• Synthesis of 2-Substituted-5-halo-2,3-dihydro-4(<i>H</i>)-pyrimidin-4-ones and Their Derivatization Utilizing the Sonogashira Coupling Reaction in the Enantioselective Synthesis of α-Substituted β-Amino Acids
  作者：Blanca R. Díaz-Sánchez、Martín A. Iglesias-Arteaga、Roberto Melgar-Fernández、Eusebio Juaristi

  DOI：10.1021/jo0705115

  日期：2007.6.1

  3-dihydro-4(H)-pyrimidin-4-ones by tandem decarboxylation/β-iodination of the corresponding 6-carboxy-perhydropyrimidin-4-ones was developed. In addition, several 1-benzoyl-2(S)-substituted-5-bromo-2,3-dihydro-4(H)-pyrimidin-4-ones were readily prepared by bromination of 1-benzoyl-2(S)-substituted-2,3-dihydro-4(H)-pyrimidin-4-ones. Subsequently, Sonogashira coupling of the halogenated heterocyclic enones with various

  通过串联脱羧/β-碘化反应合成1-苯甲酰基-2（S）-取代的5-碘-2-，3-二氢-4（H）-嘧啶-4-酮的一种便捷的一锅法开发了相应的6-羧基-全氢嘧啶-4-酮。另外，通过将1-苯甲酰基-2（S）-溴化，可以容易地制备几个1-苯甲酰基-2（S）-取代的5-溴-2,3-二氢-4（H）-嘧啶-4-酮。取代的2，3-二氢-4（H）-嘧啶-4-酮。随后，将卤代杂环烯酮与各种末端炔烃进行Sonogashira偶联，制得1-苯甲酰基-2（S）-异丙基-5-炔基-2,3-二氢-4（H）-嘧啶-4-酮，收率高。将Sonogashira产品中的不饱和C-C部分进行氢化，然后进行酸水解，即可得到高度对映体富集的α-取代的β-氨基酸。
• X-ray Crystallographic Study of Substituted Perhydropyrimidinones. Extreme Changes in Ring Conformation
  作者：Yara Ramírez-Quirós、Margarita Balderas、Jaime Escalante、Delia Quintana、Itzell Gallardo、Domingo Madrigal、Elies Molins、Eusebio Juaristi

  DOI：10.1021/jo991297q

  日期：1999.11.1

  X-ray crystal structures of 20 differently substituted perhydropyrimidin-4-ones are presented. Analysis of these data reveal a remarkable conformational sensitivity of a six-membered ring to substitution. Thus half-chair; envelope, boat, twist-boat, and intermediate conformations are found for the six-membered heterocycle, providing evidence for a relatively flat conformational energy surface in this ring, interpretation of the preferred conformations is advanced in terms of steric interactions among substituents and, in some cases, as the result of particular conformational (A(1,3) strain, anomeric) effects.
• Tandem reactions initiated by the oxidative decarboxylation of 1-benzoyl-2(S)-tert-butyl-6(S)-carboxyperhydropyrimidin-4-one
  作者：Martı́n A. Iglesias-Arteaga、C.Gabriela Avila-Ortiz、Eusebio Juaristi

  DOI：10.1016/s0040-4039(02)01066-3

  日期：2002.7

  Treatment of the title perhydropyrimidinone with diacetoxyiodobenzene and iodine followed by addition of allyltrimethylsilane and boron trifluoride etherate afforded 1-benzoyl-2(S)-tert-butyl-2,3-dihydro-4(H)-pyrimidin-4-one in 65 71% yield, via an efficient three-step radical decarboxylation-oxidation-beta-elimination tandem reaction. In contrast, when addition of allyltrimethylsilane/BF3.OEt2, was suppressed, a remarkable five-step tandem process led to the formation of vinylic iodide, 1-benzoyl-2(S)-tertbutyl-5-iodo-2,3-dihydro-4(H)-pyrimidin-4-one as the main product. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Alternative procedure for the synthesis of enantiopure 1-benzoyl-2(S)-tert-butyl-3-methylperhydropyrimidin-4-one, a useful starting material for the enantioselective synthesis of α-substituted β-amino acids
  作者：Martı́n A. Iglesias-Arteaga、Elena Castellanos、Eusebio Juaristi

  DOI：10.1016/s0957-4166(03)00048-x

  日期：2003.3

  The title heterocycle is prepared in enantiomerically pure form and in 46-50% overall yield from (S)-asparagine, a readily available starting material. The synthetic route described in this report represents a major improvement over the original procedure (Tetrahedron: Asymmetry 1991, 3, 723), that afforded a 24-32% overall yield. Furthermore, the use of toxic reagents such as Pb(OAc)(4) and dimethyl sulfate is avoided in the present protocol. (C) 2003 Published by Elsevier Science Ltd.
• An electrochemical interpretation of the mechanism of the chemical decarboxylation of 6-carboxyperhydropyrimidin-4-ones
  作者：Martı́n A. Iglesias-Arteaga、Eusebio Juaristi、Felipe J. González

  DOI：10.1016/j.tet.2004.02.052

  日期：2004.4

  The present work analyzes the anodic oxidation of the tetrabutylammonium salt of 1-benzoyl-2(S)-tert-butyl-6(S)carboxyperhydropyrimidin-4-one, which is a useful starting material in the synthesis of enantiopure alpha-substituted beta-amino acids. It was demonstrated that in CH2Cl2 solvent, the anodic oxidation reaction results in fast and complete decarboxylation, followed by proton elimination thereby leading to the same product of chemical (diacetoxyiodobenzene) oxidative decarboxylation. The electrochemical mechanism involves two electron transfer steps, but appears as a monoelectronic process owing to the release of one proton from the key acyliminium carbocation intermediate. The relative stability of this intermediate and the suppression of any solvolysis reaction in CH2Cl2 allow for the detection of the acyliminium intermediate by means of cyclic voltammetry experiments. By contrast, in the presence of a nucleophilic solvent such as acetonitrile, the acyliminium intermediate is trapped in a typical Ritter reaction. (C) 2004 Published by Elsevier Ltd.