(1S,5S)-1-(tert-butoxycarbonyl)-2-oxo-3-oxabicyclo<3.1.0>hexane | 143169-41-9

• 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: (1S,5S)-1-(tert-butoxycarbonyl)-2-oxo-3-oxabicyclo<3.1.0>hexane
• 英文别名: (1S,5S)-tert-butyl 2-oxo-3-oxabicyclo[3.2.1]hexane-1-carboxylate；tert-butyl (1S,5S)-2-oxo-3-oxabicyclo[3.1.0]hexane-1-carboxylate
• CAS: 143169-41-9
• 化学式: C₁₀H₁₄O₄
• 分子量: 198.219
• InChiKey: FMBVDGFTHXLKLF-LDWIPMOCSA-N

物化性质

• 沸点：
  301.0±25.0 °C(Predicted)
• 密度：
  1.262±0.06 g/cm3(Predicted)

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：

  (1S,5S)-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 (1S,2S)-(-)-1--2-(mercaptomethyl)cyclopropane-1-caronitrile
  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：

  (2R)-glycidyl triflate 、 丙二酸二叔丁酯 在 15-冠醚-5 、 sodium hydride 作用下， 生成 (1S,5S)-1-(tert-butoxycarbonyl)-2-oxo-3-oxabicyclo<3.1.0>hexane
  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

文献信息

• Constrained analogs of methionine: asymmetric synthesis of χ-angle restricted methionine derivatives through [3.1.0]-γ-lactone cyclopropane ring opening
  作者：Chang-Sun Lee、Kee-In Lee、Andrew D Hamilton

  DOI：10.1016/s0040-4039(00)01912-2

  日期：2001.1

  Regiospecific and stereoselective ring opening of a [3.1.0]-γ-lactone intermediate by sulfur-containing nucleophiles has been developed. The reaction product was confirmed by NMR techniques and chemical equilibrium processes. Using this approach, all four possible diastereomers of χ-angle restricted methionine surrogates have been synthesized by electrophilic azidation and reduction to the amino group

  已经开发了含硫亲核试剂对[3.1.0]-γ-内酯中间体的区域特异性和立体选择性开环。反应产物通过NMR技术和化学平衡过程确认。使用这种方法，已经通过亲电子叠氮并将其还原为氨基，合成了4种可能的x角受限的蛋氨酸替代物的非对映异构体。这些受约束的类似物可用于制备在C-末端位置含有蛋氨酸的序列的拟肽。
• Large Scale Syntheses of N-Protected 2,3-Methanomethionine Stereoisomers
  作者：Kevin Burgess、Chun-Yen Ke

  DOI：10.1055/s-1996-4425

  日期：1996.12

  Three stereoisomers of N-protected forms of 2,3-methanomethionine (cyclopropyl derivatives of methionine, or ”cyclo-Met”) were prepared. Two of the syntheses developed involved diol (S)-1, which was more easily obtained from L-gulono-1,4-lactone than via juxtaposition of the benzyl protection of (R)-1. The cis-cyclo-Met derivative (cis refers to the orientation of the side chain relative to the amino functionality), FMOC-(2R,3S)-cyclo-Met, was obtained via a route based on a previous synthesis of (2R,3S)-cyclo-Met from the lactone 3, but the protected trans-cyclo-Met, BOC-(2R,3S)-cyclo-Met, was obtained via an improved procedure that does not involve lactone 3.

  我们制备了三种 2,3-甲硫氨酸 N 保护形式的立体异构体（甲硫氨酸的环丙基衍生物，或称 "环甲硫氨酸"）。其中两种合成涉及二元醇 (S)-1，它更容易从 L-古洛萘-1,4-内酯中获得，而不是通过并置苄基保护的 (R)-1。顺式环-Met 衍生物（顺式指侧链相对于氨基官能团的取向）FMOC-(2R,3S)-环-Met 是通过以前从内酯 3 合成 (2R,3S)-cyclo-Met 的路线获得的，但受保护的反式环-Met BOC-(2R,3S)-cyclo-Met 则是通过一种不涉及内酯 3 的改进程序获得的。
• 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。
• Müller, Paul; Boléa, Christelle, Synlett, 2000, # 6, p. 826 - 828
  作者：Müller, Paul、Boléa, Christelle

  DOI：——

  日期：——
• Asymmetric syntheses of all four stereoisomers of 2,3-methanomethionine
  作者：Kevin Burgess、Kwok Kan Ho

  DOI：10.1021/jo00048a028

  日期：1992.10

  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.