tert-butyl (1S,2S)-1-carbamoyl-2-(hydroxymethyl)cyclopropane-1-carboxylate | 146400-27-3

• 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: tert-butyl (1S,2S)-1-carbamoyl-2-(hydroxymethyl)cyclopropane-1-carboxylate
• CAS: 146400-27-3
• 化学式: C₁₀H₁₇NO₄
• 分子量: 215.249
• InChiKey: GYFDHLMTYDJFPG-LDWIPMOCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.19
• 重原子数：
  15.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  89.62
• 氢给体数：
  2.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  tert-butyl (1S,2S)-1-carbamoyl-2-(hydroxymethyl)cyclopropane-1-carboxylate 在 吡啶 、 咪唑 、 lead(IV) acetate 作用下， 以 二氯甲烷 为溶剂， 生成 1-(tert-Butoxycarbonyl)-1-<(tert-butoxycarbonyl)amino>-2-<<(tert-butyldimethylsilyl)oxy>methyl>cyclopropane
  参考文献：
  名称：

  Intramolecular cyclopropanation: stereospecific synthesis of (E)- and (Z)-1-aminocyclopropane-1-carboxylic acids

  摘要：

  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.

  DOI：

  10.1021/jo00056a020
• 作为产物：
  描述：

  丙二酸单叔丁酯 在 triethylphosphite copper(I) iodide complex 甲醇 、 4-二甲氨基吡啶 、 对甲苯磺酰叠氮 、 氨 、 potassium carbonate 、 N,N'-二环己基碳二亚胺 作用下， 以 甲苯 、 乙腈 为溶剂， 反应 6.0h， 生成 tert-butyl (1S,2S)-1-carbamoyl-2-(hydroxymethyl)cyclopropane-1-carboxylate
  参考文献：
  名称：

  Intramolecular cyclopropanation: stereospecific synthesis of (E)- and (Z)-1-aminocyclopropane-1-carboxylic acids

  摘要：

  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.

  DOI：

  10.1021/jo00056a020

文献信息

• 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。
• 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
• 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.
• Asymmetric syntheses of protected derivatives of ornithine- and arginine-2,3-methanologs
  作者：Kevin Burgess、Kwok-Kan Ho

  DOI：10.1016/0040-4039(92)89003-u

  日期：1992.9

  Bicyclic lactone 2 has been used as a starting material for preparations of st