O-{1-(4-methoxyphenyl)-but-3-enyl}-N-(tert-butyloxycarbonyl)hydroxylamine | 877172-21-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: O-{1-(4-methoxyphenyl)-but-3-enyl}-N-(tert-butyloxycarbonyl)hydroxylamine
• 英文别名: (+/-)-tert-butyl 1-(4-methoxyphenyl)but-3-enyloxycarbamate；(+/-)-tert-butyl {[1-(4-methoxyphenyl)-3-butene-1-yl]oxy}carbamate；tert-butyl N-[1-(4-methoxyphenyl)but-3-enoxy]carbamate
• CAS: 877172-21-9
• 化学式: C₁₆H₂₃NO₄
• 分子量: 293.363
• InChiKey: XZKJPFHMVANXFA-UHFFFAOYSA-N

物化性质

• 密度：
  1.061±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  21
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  56.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  O-{1-(4-methoxyphenyl)-but-3-enyl}-N-(tert-butyloxycarbonyl)hydroxylamine 、 溴苯 在 tris(dibenzylideneacetone)dipalladium (0) 、 sodium t-butanolate 、 tri tert-butylphosphoniumtetrafluoroborate 作用下， 以 甲苯 为溶剂， 反应 2.5h， 以74%的产率得到(+/-)-(3S*,5S*)-tert-butyl 3-benzyl-5-(4-methoxyphenyl)isoxazolidine-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-(4-甲氧苯基)-1-丁烯-4-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-(4-methoxyphenyl)-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

• Stereoselective Palladium-Catalyzed Functionalization of Homoallylic Alcohols: A Convenient Synthesis of Di- and Trisubstituted Isoxazolidines and β-Amino-δ-Hydroxy Esters
  作者：Andrei V. Malkov、Maciej Barłóg、Lucie Miller-Potucká、Mikhail A. Kabeshov、Louis J. Farrugia、Pavel Kočovský

  DOI：10.1002/chem.201102716

  日期：2012.5.29

  Enantiopure, Boc‐protected alkoxyamines 12 and 13, derived from the readily available homoallylic alcohols 4 via a reaction that involves either inversion or retention of configuration, undergo a diastereoselective Pd‐catalyzed ring‐closing carbonylative amidation to produce isoxazolidines 16/17 (≤50:1 diastereoisomer ratio (d.r.)) that can be readily converted into the N‐Boc‐protected esters of β‐amino‐δ‐hydroxy

  对映体纯的Boc保护的烷氧基胺12和13通过易于转化的或保留构型的反应从易得的均丙醇4衍生而来，进行非对映选择性的Pd催化的闭环羰基酰胺化反应生成异恶唑烷16/17（≤50 1：1的非对映异构体比率（dr）可以很容易地转化为N -Boc保护的β-氨基-δ-羟基酸的酯及其γ取代的同系物37。关键的羰基化环化过程是通过跨CC键的钯和氮亲核试剂的不寻常的顺式加成而进行的（19 → 21），如15的反应所揭示，得到具有高非对映选择性的异恶唑烷18。
• 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.