(1R,5R)-(-)-1-(tert-butoxycarbonyl)-2-oxo-3-oxabicyclo<3.1.0>hexane | 143169-40-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (1R,5R)-(-)-1-(tert-butoxycarbonyl)-2-oxo-3-oxabicyclo<3.1.0>hexane
• 英文别名: tert-butyl (1R,5R)-2-oxo-3-oxabicyclo[3.1.0]hexane-1-carboxylate
• CAS: 143169-40-8
• 化学式: C₁₀H₁₄O₄
• 分子量: 198.219
• InChiKey: FMBVDGFTHXLKLF-QUBYGPBYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1R,5R)-(-)-1-(tert-butoxycarbonyl)-2-oxo-3-oxabicyclo<3.1.0>hexane 在 吡啶 、 4-二甲氨基吡啶 、 ammonium hydroxide 、 叠氮磷酸二苯酯 、 potassium carbonate 、 caesium carbonate 、 三乙胺 、 对甲苯磺酰氯 、 三氟乙酸 作用下， 以 甲醇 、 二氯甲烷 、 乙腈 为溶剂， 反应 74.83h， 生成 (1R,2R)-(+)-1--2-(mercaptomethyl)cyclopropane-1-carbonitrile
  参考文献：
  名称：

  Asymmetric syntheses of all four stereoisomers of 2,3-methanomethionine

  摘要：

  Asymmetric syntheses of all four stereoisomers of 2,3-methanomethionine ((Z)- and (E)-cyclo-Met) are described. The source of chirality in these reactions is the trifluoromethylsulfonate ester 1b which reacts with di-tert-butyl malonate via direct displacement of trifluoromethylsulfonate followed by lactonization to give 1-(tert-butoxycarbonyl)-2-oxo-3-oxabicyclo[3.1.0]hexane (2). Conversion of compound 2 into (Z)-cyclo-Met can be achieved via ring opening of the lactone, Hoffmann rearrangement, mesylation, and displacement with thiomethoxide. A route to (E)-cyclo-Met was developed using a lipase to effect a critical ester hydrolysis.

  DOI：

  10.1021/jo00048a028
• 作为产物：
  描述：

  丙二酸二叔丁酯 在 palladium on activated charcoal 氢气 、 sodium hydride 、 对甲苯磺酸 作用下， 以 乙二醇二甲醚 、 氯仿 、 乙酸乙酯 为溶剂， 生成 (1R,5R)-(-)-1-(tert-butoxycarbonyl)-2-oxo-3-oxabicyclo<3.1.0>hexane
  参考文献：
  名称：

  Synthesis and Biological Evaluation of 1-Amino-2-Phosphonomethylcyclopropanecarboxylic Acids, New Group III Metabotropic Glutamate Receptor Agonists

  摘要：

  Stereoisomers of 1-amino-2-phosphonomethylcyclopropanecarboxylic acid (APCPr), conformationally restricted analogues of L-AP4 (2-amino-4-phosphonobutyric acid), have been prepared and evaluated at recombinant group III metabotropic glutamate receptors. They activate these receptors over a broad range of potencies. The most potent isomer (1S,2R)-APCPr displays a similar pharmacological profile as that of L-AP4 (EC50 0.72, 1.95, > 500, 0.34 mu M at mGlu4, 6, 7, 8 receptors, respectively, and no effect at group I/II mGluRs). It was characterized on native receptors located in the basal ganglia (BG) where it induced a robust and reversible inhibition of synaptic transmission. It was tested in vivo in haloperidol-induced catalepsy, a model of Parkinsonian akinesia, by direct infusion in the globus pallidus of the BG. At a dose of 0.5 nmol/mu L, catalepsy was significantly antagonized. This study reveals that (1S,2R)-APCPr is a potent group III mGluR agonist and confirms that these receptors may be considered as a therapeutic target in the Parkinson's disease.

  DOI：

  10.1021/jm070262c

文献信息

• Carbenoid Pathways in Copper-Catalyzed Intramolecular Cyclopropanations of Phenyliodonium Ylides
  作者：Paul Müller、Christelle Boléa

  DOI：10.1002/1522-2675(20010516)84:5<1093::aid-hlca1093>3.0.co;2-t

  日期：2001.5.16

  cyclopropanation of allyl diazomalonates and the corresponding phenyliodonium ylides was investigated with a series of chiral, non-racemic ligands. The reaction of 6b in the presence of the bis[dihydrooxazole] ligand Xa in refluxing 1,2-dichloroethane proceeded to 8b with an enantiomer excess (ee) of up to 72% under optimized conditions. In contrast, 8b resulting from reaction of ylide 7b with the same

  用一系列手性非外消旋配体研究了铜催化的重氮丙二酸烯丙酯分子内环丙烷化反应和相应的苯基碘叶立德的对映选择性。6b 在双[二氢恶唑] 配体 Xa 存在下在回流的 1,2-二氯乙烷中的反应进行到 8b，在优化条件下对映异构体过量 (ee) 高达 72%。相比之下，由叶立德 7b 与相同配体反应产生的 8b，但在 0°的 CH2Cl2 中，ee 仅为 30%。然而，与其他配体相比，重氮丙二酸酯 6b 的对映选择性低于内立德 7b。乙酰乙酸衍生的苯基碘鎓叶立德 15b 的分子内环丙烷化得到具有 68% ee 和配体 Xa 的 16b，但相应的重氮化合物在暴露于手性铜催化剂时不反应。叶立德 7 和 15 的 Cu 催化反应中不对称诱导的观察与类卡宾机制一致；然而，在重氮丙二酸 6b 和叶立德 7b 之间观察到的对映选择性的差异表明，在铜的配位范围之外，环丙烷化的竞争性非选择性途径。
• Unusually large reactivity differences in the transformation of cyclopropane lactones to 1-aminocyclopropane-1-phosphonic acids and their carboxylic acid analogues
  作者：Zsuzsa M. Jászay、György M. Keserű、György Clementis、Imre Petneházy、Katalin Kováts、László Tőke

  DOI：10.1002/hc.5

  日期：——

  cyclopropane lactone 5, the synthesis of a 1-aminocyclopropane-1-phosphonic acid derivative 11 is described. The considerable differences in the reactivity of the lactone ring opening in the case of a cyclopropane lactone substituted by a phosphonic acid ester 5 and their carboxylic acid ester analogue 2 toward ammonia or amines have been compared and interpreted by using the map of electrostatic potentials

  从环丙烷内酯 5 开始，描述了 1-氨基环丙烷-1-膦酸衍生物 11 的合成。在环丙烷内酯被膦酸酯 5 和它们的羧酸酯类似物 2 取代的情况下，内酯开环的反应性对氨或胺的显着差异已经通过使用静电势图进行了比较和解释。© 2001 John Wiley & Sons, Inc. 杂原子化学 12:90–96, 2001
• Intramolecular cyclopropanation: stereospecific synthesis of (E)- and (Z)-1-aminocyclopropane-1-carboxylic acids
  作者：Ari M. P. Koskinen、Luis Munoz

  DOI：10.1021/jo00056a020

  日期：1993.2

  tert-Butyl-substituted allyl malonates, prepared in two steps from malonic acid, are diazotized in high yields. The diazomalonates 7 undergo a stereospecific copper(I)-catalyzed cyclopropanation to give 1-(tert-butoxycarbonyl)-3-oxa-2-oxobicyclo[3.1.0]hexanes 8 which can be converted to the protected (E)- or (Z)-1-aminocyclopropane-1-carboxylic acids 10 or 15 via Curtius- or Hoffmann-type rearrangements, respectively. The sequences are short (six steps from malonic acid) and proceed with good overall yields (20-40% overall from malonic acid) The free amino acids 12 and 18 can be liberated in two steps.
• Synthesis of a valuable cyclopropyl chiron for preparations of 2,3-methanoamino acids
  作者：Kevin Burgess、Kwok Kan Ho、Chun Yen Ke

  DOI：10.1021/jo00066a033

  日期：1993.7
• Müller, Paul; Boléa, Christelle, Synlett, 2000, # 6, p. 826 - 828
  作者：Müller, Paul、Boléa, Christelle

  DOI：——

  日期：——