N-(tert-butoxycarbonyl)-15N-hydroxylamine | 144181-77-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机碳酸及其衍生物
• 英文名称: N-(tert-butoxycarbonyl)-15N-hydroxylamine
• 英文别名: tert-butyl [¹⁵N]-N-hydroxycarbamate；15N-tert-butoxycarbonyl hydroxylamine；(15)N-t-butoxycarbonylhydroxylamine；Boc(15)NHOH
• CAS: 144181-77-1
• 化学式: C₅H₁₁NO₃
• 分子量: 134.141
• InChiKey: DRDVJQOGFWAVLH-PTQBSOBMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  9.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  58.56
• 氢给体数：
  2.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  苯酐 、 N-(tert-butoxycarbonyl)-15N-hydroxylamine 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 4.17h， 以35%的产率得到C₁₃H₁₅⁽¹⁵⁾NO₆
  参考文献：
  名称：

  Kinetics of Action of a Two-Stage Pro-Inhibitor of Serine β-Lactamases

  摘要：

  beta-Lactamase inhibitors are important in medicine in the protection of beta-lactam antibiotics from beta-lactamase-catalyzed destruction. The most effective inhibitors of serine beta-lactamases covalently modify the enzyme active site. We have recently studied O-acyl and O-phosphyl hydroxamates as a new class of such inhibitors. In this paper, we describe our studies of the N-acyl derivatives of a cyclic O-acyl hydroxamic acid, 3H-benzo[d][1,2]oxazine-1,4-dione, and, in particular, the N-tert-butoxycarbonyl derivative. This compound is not a beta-lactamase inhibitor itself but undergoes spontaneous hydrolysis in aqueous solution, yielding an O-phthaloyl hydroxamic acid, which is a beta-lactamase inhibitor. This compound spontaneously, but reversibly, cyclizes in solution to form phthalic anhydride, which is also a beta-lactamase inhibitor. Both inhibitors react to form the same transiently stable phthaloyl-enzyme complex. Thus, we have a two-step cascade, beginning with a pro-inhibitor, in which each step leads to a different inhibitor, presumably with different enzyme specificities. The kinetics of these transformations have been elucidated in detail. The phthaloyl derivatives, where the free carboxylate is important for facile reaction with the enzyme, represent a new lead for serine beta-lactamase inhibitors. Analogues can be conveniently constructed in situ by reaction of nucleophiles with phthalic anhydrides and then screened for activity. Active hits may then become new leads.

  DOI：

  10.1021/bi400873r
• 作为产物：
  描述：

  二碳酸二叔丁酯 在 ¹⁵N-hydroxylamine 、 potassium carbonate 作用下， 以 乙醚 、 水 为溶剂， 以73%的产率得到N-(tert-butoxycarbonyl)-15N-hydroxylamine
  参考文献：
  名称：

  山梨酸酯衍生物的酰基亚硝基Diels–Alder（ANDA）反应：X射线和15 N NMR研究及其在氨基酸合成中的应用†

  摘要：

  我们使用烷氧基羰基亚硝基二烯亲和体，对山梨酸酯和山梨醇衍生物的酰基亚硝基Diels-Alder（ANDA）反应进行了研究。反应条件的优化山梨酸乙酯 首先介绍，并将该产品用于高效合成 5-甲基鸟氨酸。山梨醇的结构反应性趋势（E，E -2,4-己二-1-醇）及其酰化类似物，然后进行讨论。我们提供了两个系列中关键加合物的单晶X射线结构证明，并详细介绍了一种新颖的HMBC / HSQC（1 H– 15 N）判据，用于容易地区分由此类ANDA反应引起的区域异构体。

  DOI：

  10.1039/b912963d

文献信息

• Syntheses of structurally diverse amino acids, including δ-hydroxylysine, using the acyl nitroso Diels–Alder reaction
  作者：Lee Bollans、John Bacsa、Daniel A. O’Farrell、Scott Waterson、Andrew V. Stachulski

  DOI：10.1016/j.tetlet.2010.02.076

  日期：2010.4

  with fully controlled relative stereochemistry, the acyl nitroso Diels–Alder (ANDA) reaction is ideally suited to the synthesis of structurally diverse, including hydroxylated, amino acids. The major issue to be tackled is that of regiochemistry in the ANDA addition to unsymmetrical dienes. The transformation of three diverse types of ANDA adducts into amino acids is described, in particular, the synthesis

  借助亚硝基Diels-Alder（ANDA）反应，它可以在完全受控的相对立体化学条件下以1,4-关系引入氨基和羟基官能团，因此非常适合合成结构多样的氨基酸，包括羟基化的氨基酸。要解决的主要问题是除不对称二烯外的ANDA中的区域化学问题。描述了三种不同类型的ANDA加合物向氨基酸的转化，特别是作为保护形式的单一（2 SR，5 SR）非对映异构体，δ-羟基赖氨酸（胶原的重要组成部分）的合成。
• Synthesis of chiral isoxazolidin-5-ones and their applications to the synthesis of β-amino-alanines and β-(N-hydroxyamino)-alanines
  作者：Jack E. Baldwin、Robert M. Adlington、Lisa C. Mellor

  DOI：10.1016/s0040-4020(01)90416-8

  日期：1994.4

  Herein we report a high-yielding synthesis of isoxazolidin-5-ones and their use to synthesise both β-amino-alanines and β-(N-hydroxyamino)-alanines.

  在本文中，我们报道了高产的异恶唑烷丁5-酮的合成及其在合成β-氨基丙氨酸和β-（N-羟基氨基）-丙氨酸中的用途。
• Acid-catalyzed amino-migration of O-phenylhydroxylamines
  作者：Naoki Haga、Yasuyuki Endo、Kenichiro Kataoka、Kentaro Yamaguchi、Koichi Shudo

  DOI：10.1021/ja00051a012

  日期：1992.12

  The mechanism of amino-migration of O-phenylhydroxylamine (1a) was studied. It was found that 1 rearranges to give 2-aminophenol (50%) and 4-aminophenol (7%) in trifluoroacetic acid (TFA). The predominance of the ortho rearrangement of 1 clearly distinguishes this process from the Bamberger rearrangement. From cross-coupling experiments employing stable isotopes, it was clarified that the ortho rearrangement proceeds intramolecularly and the para rearrangement involves both intra- and intermolecular processes. Good first-order kinetics were obtained for the rearrangement. The Hammett plot (sigma+) with a large negative slope (rho = -7.8) indicates that initial heterolytic N-O bond cleavage of 1 occurs and generates a positive charge on the oxygen atom with considerable delocalization into the aromatic ring. An ion-molecule pair involving a phenoxenium ion and an ammonia molecule as an intermediate rationalizes all of the results. In this pair, intramolecular combination to the ortho position proceeds preferentially over that to the para position. Formation of catechol and hydroquinone can be explained in terms of nucleophilic attack of TFA on the phenoxenium ion in a solvent-separated pair.