4-methylenehex-5-en-1-yl hydroxycarbamate | 845556-00-5

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 4-methylenehex-5-en-1-yl hydroxycarbamate
• 英文别名: 4-methylene-4-pentane N-hydroxycarbamate；4-methylidenehex-5-enyl N-hydroxycarbamate
• CAS: 845556-00-5
• 化学式: C₈H₁₃NO₃
• 分子量: 171.196
• InChiKey: NNYILNPRSWHASO-UHFFFAOYSA-N

物化性质

• 沸点：
  332.2±21.0 °C(Predicted)
• 密度：
  1.067±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  12
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  58.6
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-methylenehex-5-en-1-yl hydroxycarbamate 在 叔丁基过氧化氢 、 rac-cyclohexan-1,2-bis(-N=C-C₆H₃-5-NO₂-2-O-)Ru(PPh₃)2 作用下， 以 正己烷 、 二氯甲烷-D2 为溶剂， 生成 3,10-dioxa-1-azabicyclo[5.3.1]undec-7-en-2-one
  参考文献：
  名称：

  过渡金属催化的羟基亚硝基衍生物原位Diels-Alder诱捕的过渡金属催化的羟肟酸氧化机理

  摘要：

  提出了新的见解，介绍了过渡金属介导的异羟肟酸氧化产生中间体酰基亚硝基物质的机理，以及随后的杂Diels-Alder捕集。研究了三苯基膦连接的钌-salen配合物的活化，并提供了涉及异羟肟酸氧化过程的钌-氧代物种的证据。解释了观察到的中间分子酰基亚硝基物种涉及的分子间环加成过程中缺乏不对称诱导的现象，并通过比较了钌-salen-基体系与亚硝基甲苯，铜（I）/铜（II）BINAP-催化的亚硝基吡啶配合物。

  DOI：

  10.1002/adsc.200700568
• 作为产物：
  描述：

  ethyl 4-methylenehex-5-enoate 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 5.5h， 生成 4-methylenehex-5-en-1-yl hydroxycarbamate
  参考文献：
  名称：

  Dual Function Catalysts. Dehydrogenation and Asymmetric Intramolecular Diels−Alder Cycloaddition of N-Hydroxy Formate Esters and Hydroxamic Acids:  Evidence for a Ruthenium−Acylnitroso Intermediate

  摘要：

  The chiral ruthenium salen complex, 13b, functions as an efficient catalyst for the sequential oxidation and asymmetric Diels-Alder cycloaddition of hydroxamic acids and N-hydroxy formate esters. This result provides evidence for the formation of a ruthenium-nitroso formate (acyl nitroso) intermediate. The Diels-Alder precursors are prepared from simple building blocks, and the cycloadducts, bridged oxazinolactams, can serve as useful intermediates in organic synthesis.

  DOI：

  10.1021/ja050059b

文献信息

• Copper(II)-Catalyzed Room Temperature Aerobic Oxidation of Hydroxamic Acids and Hydrazides to Acyl-Nitroso and Azo Intermediates, and Their Diels–Alder Trapping
  作者：Duangduan Chaiyaveij、Leah Cleary、Andrei S. Batsanov、Todd B. Marder、Kenneth J. Shea、Andrew Whiting

  DOI：10.1021/ol201188d

  日期：2011.7.1

  2-ethyl-2-oxazoline ligand, is an effective catalyst for the room temperature, aerobic oxidation of hydroxamic acids and hydrazides, to acyl-nitroso and azo dienophiles respectively, which are efficiently trapped in situ via both inter- and intramolecular hetero-Diels–Alder reactions with dienes. Both inter- and intramolecular variants of the Diels–Alder reaction are suitable under the reaction conditions using a variety

  在存在2-乙基-2-恶唑啉配体的情况下，CuCl 2是一种有效的催化剂，可用于室温下氧肟酸和酰肼的好氧氧化，分别生成酰基亚硝基和偶氮二亲二苯并通过原位有效捕获。分子间和分子内异狄尔斯-阿尔德反应与二烯。Diels–Alder反应的分子间和分子内变体都适用于使用多种溶剂的反应条件。在相同条件下，酰肼也被氧化，得到酰基偶氮二亲二烯体，其被二烯分子内捕获。
• Mechanistic Insights into Transition Metal-Catalysed Oxidation of a Hydroxamic Acid within situ Diels–Alder Trapping of the Acyl Nitroso Derivative
  作者：Judith A. K. Howard、Gennadiy Ilyashenko、Hazel A. Sparkes、Andrew Whiting、Allen R. Wright

  DOI：10.1002/adsc.200700568

  日期：2008.4.7

  New insights into the mechanism for the transition metal-mediated oxidation of hydroxamic acids to give intermediate acyl nitroso species, with subsequent hetero-Diels–Alder trapping are presented. The activation of triphenylphosphine-ligated ruthenium-salen complexes is examined, and evidence is presented for the ruthenium-oxo species which are involved in the oxidative process of the hydroxamic acid

  提出了新的见解，介绍了过渡金属介导的异羟肟酸氧化产生中间体酰基亚硝基物质的机理，以及随后的杂Diels-Alder捕集。研究了三苯基膦连接的钌-salen配合物的活化，并提供了涉及异羟肟酸氧化过程的钌-氧代物种的证据。解释了观察到的中间分子酰基亚硝基物种涉及的分子间环加成过程中缺乏不对称诱导的现象，并通过比较了钌-salen-基体系与亚硝基甲苯，铜（I）/铜（II）BINAP-催化的亚硝基吡啶配合物。
• Dual Function Catalysts. Dehydrogenation and Asymmetric Intramolecular Diels−Alder Cycloaddition of <i>N</i>-Hydroxy Formate Esters and Hydroxamic Acids:  Evidence for a Ruthenium−Acylnitroso Intermediate
  作者：Chun P. Chow、Kenneth J. Shea

  DOI：10.1021/ja050059b

  日期：2005.3.1

  The chiral ruthenium salen complex, 13b, functions as an efficient catalyst for the sequential oxidation and asymmetric Diels-Alder cycloaddition of hydroxamic acids and N-hydroxy formate esters. This result provides evidence for the formation of a ruthenium-nitroso formate (acyl nitroso) intermediate. The Diels-Alder precursors are prepared from simple building blocks, and the cycloadducts, bridged oxazinolactams, can serve as useful intermediates in organic synthesis.