O-(1-methyl-but-3-enyl)-N-(tert-butyloxycarbonyl)hydroxylamine | 877172-26-4

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: O-(1-methyl-but-3-enyl)-N-(tert-butyloxycarbonyl)hydroxylamine
• 英文别名: (+/-)-tert-butyl pent-4-en-2-yloxycarbamate；tert-butyl N-pent-4-en-2-yloxycarbamate
• CAS: 877172-26-4
• 化学式: C₁₀H₁₉NO₃
• 分子量: 201.266
• InChiKey: YVRFYYUNQWYQNE-UHFFFAOYSA-N

物化性质

• 密度：
  0.968±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  47.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  O-(1-methyl-but-3-enyl)-N-(tert-butyloxycarbonyl)hydroxylamine 、 4-溴苯甲醚 在 tris(dibenzylideneacetone)dipalladium (0) 、 sodium t-butanolate 、 tri tert-butylphosphoniumtetrafluoroborate 作用下， 以 甲苯 为溶剂， 反应 6.0h， 以70%的产率得到(+/-)-tert-butyl 3-(4-methoxybenzyl)-5-methylisoxazolidine-2-carboxylate
  参考文献：
  名称：

  Influence of Hydroxylamine Conformation on Stereocontrol in Pd-Catalyzed Isoxazolidine-Forming Reactions

  摘要：

  Palladium-catalyzed carboamination reactions between N-Boc-O-(but-3-enyl)hydroxylamine derivatives and aryl or alkenyl bromides afford cis-3,5- and trans-4,5-disubstituted isoxazolidines in good yield with up to >20:1 dr. The diastercoselectivity observed in the formation of cis-3,5-disubstituted isoxazolidines is superior to selectivities typically obtained in other transformations, such as 1,3-dipolar cycloaddition reactions, that provide these products. In addition, the stereocontrol in the C-N bond-forming Pd-catalyzed carboamination reactions of N-Boc-O-(but-3-enyl)hydroxylamines is significantly higher than that of related C-O bond-forming carboetherification reactions of N-benzyl-N-(but-3-enyl)hydroxylamine derivatives. This is likely due to a stereoelectronic preference for cyclization via transition states in which the Boc group is placed in a perpendicular orientation relative to the plane of the developing ring, which derives from the conformational equilibria of substituted hydroxylamines.

  DOI：

  10.1021/jo8027399
• 作为产物：
  描述：

  4-戊烯-2-醇 在 sodium hydroxide 、 一水合肼 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 O-(1-methyl-but-3-enyl)-N-(tert-butyloxycarbonyl)hydroxylamine
  参考文献：
  名称：

  Palladium(0)-catalyzed cascade one-pot synthesis of isoxazolidines

  摘要：

  A highly diastereoselective cascade reaction protocol has been developed for the synthesis of isoxazolidine derivatives utilizing aryl halides, O-homoallyl hydroxylamine and palladium(0) in a one-pot reaction. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2005.11.148

文献信息

• Palladium(II)‐Catalyzed Synthesis of Isoxazolidines: Using a Catalytic Copper Acetate and Molecular Oxygen as the Cooxidant
  作者：Boon Ying Tay、Kai Xiang、Thies Thiemann、Krishna Gopal Dongol

  DOI：10.1080/00397910500516233

  日期：2006.5

  An environmentally friendly process is reported for the palladium(II)-catalyzed cyclofunctionalization of allylic hydroxylamine derivatives using a catalytic amount of copper(II) acetate and molecular oxygen as the cooxidant.
• Influence of Hydroxylamine Conformation on Stereocontrol in Pd-Catalyzed Isoxazolidine-Forming Reactions
  作者：Georgia S. Lemen、Natalie C. Giampietro、Michael B. Hay、John P. Wolfe

  DOI：10.1021/jo8027399

  日期：2009.3.20

  Palladium-catalyzed carboamination reactions between N-Boc-O-(but-3-enyl)hydroxylamine derivatives and aryl or alkenyl bromides afford cis-3,5- and trans-4,5-disubstituted isoxazolidines in good yield with up to >20:1 dr. The diastercoselectivity observed in the formation of cis-3,5-disubstituted isoxazolidines is superior to selectivities typically obtained in other transformations, such as 1,3-dipolar cycloaddition reactions, that provide these products. In addition, the stereocontrol in the C-N bond-forming Pd-catalyzed carboamination reactions of N-Boc-O-(but-3-enyl)hydroxylamines is significantly higher than that of related C-O bond-forming carboetherification reactions of N-benzyl-N-(but-3-enyl)hydroxylamine derivatives. This is likely due to a stereoelectronic preference for cyclization via transition states in which the Boc group is placed in a perpendicular orientation relative to the plane of the developing ring, which derives from the conformational equilibria of substituted hydroxylamines.
• Palladium(0)-catalyzed cascade one-pot synthesis of isoxazolidines
  作者：Krishna Gopal Dongol、Boon Ying Tay

  DOI：10.1016/j.tetlet.2005.11.148

  日期：2006.2

  A highly diastereoselective cascade reaction protocol has been developed for the synthesis of isoxazolidine derivatives utilizing aryl halides, O-homoallyl hydroxylamine and palladium(0) in a one-pot reaction. (c) 2005 Elsevier Ltd. All rights reserved.