N-tert-butoxycarbonyl-1-(tert-butyl)but-3-enamine

• 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: N-tert-butoxycarbonyl-1-(tert-butyl)but-3-enamine
• 英文别名: (±)-tert-butyl (2,2-dimethylhex-5-en-3-yl)carbamate；tert-butyl (2,2-dimethylhex-5-en-3-yl)carbamate；N-Boc-(+/-)-2-dimethyl-hex-5-ene-3-amine；tert-butyl N-(2,2-dimethylhex-5-en-3-yl)carbamate
• 化学式: C₁₃H₂₅NO₂
• 分子量: 227.347
• InChiKey: ARXLIYMDVXEQHJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-tert-butoxycarbonyl-1-(tert-butyl)but-3-enamine 在 [1,2-bis-(phenylsulfinyl)ethane]palladium(II) acetate 、 磷酸二丁酯 、 对苯醌 作用下， 以 1,4-二氧六环 为溶剂， 反应 24.0h， 以77%的产率得到(±)-(4R,5R)-4-(tert-butyl)-5-vinyloxazolidin-2-one
  参考文献：
  名称：

  N-Boc Amines to Oxazolidinones via Pd(II)/Bis-sulfoxide/Brønsted Acid Co-Catalyzed Allylic C–H Oxidation

  摘要：

  A Pd(II)/bis-sulfoxide/Bronsted acid catalyzed allylic C-H oxidation reaction for the synthesis of oxazolidinones from simple N-Boc amines is reported. A range of oxazolidinones are furnished in good yields (avg 63%) and excellent diastereoselectivities (avg 15:1) to furnish products regioisomeric from those previously obtained using allylic C-H amination reactions. Mechanistic studies suggest the role of the phosphoric acid is to furnish a Pd(II)bis-sulfoxide phosphate catalyst that promotes allylic C-H cleavage and pi-allylPd functionalization with a weak, aprotic oxygen nucleophile and to assist in catalyst regeneration.

  DOI：

  10.1021/ja506036q
• 作为产物：
  描述：

  3,3-二甲基-1-丁酸 在 N,N-二甲基丙烯基脲 、 sodium azide 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 生成 N-tert-butoxycarbonyl-1-(tert-butyl)but-3-enamine
  参考文献：
  名称：

  N-Boc Amines to Oxazolidinones via Pd(II)/Bis-sulfoxide/Brønsted Acid Co-Catalyzed Allylic C–H Oxidation

  摘要：

  A Pd(II)/bis-sulfoxide/Bronsted acid catalyzed allylic C-H oxidation reaction for the synthesis of oxazolidinones from simple N-Boc amines is reported. A range of oxazolidinones are furnished in good yields (avg 63%) and excellent diastereoselectivities (avg 15:1) to furnish products regioisomeric from those previously obtained using allylic C-H amination reactions. Mechanistic studies suggest the role of the phosphoric acid is to furnish a Pd(II)bis-sulfoxide phosphate catalyst that promotes allylic C-H cleavage and pi-allylPd functionalization with a weak, aprotic oxygen nucleophile and to assist in catalyst regeneration.

  DOI：

  10.1021/ja506036q

文献信息

• Indium-Mediated Asymmetric Barbier-Type Allylation of Aldimines in Alcoholic Solvents:  Synthesis of Optically Active Homoallylic Amines
  作者：Tirayut Vilaivan、Chutima Winotapan、Vorawit Banphavichit、Tetsuro Shinada、Yasufumi Ohfune

  DOI：10.1021/jo0477244

  日期：2005.4.1

  Chiral aldimines derived from phenylglycinol were diastereoselectively allylated with indium powder/allyl bromide in alcoholic solvents. Both aliphatic and aromatic aldimines provided good yield of the desired products with high diastereoselectivity. A racemization-free protocol for removal of the phenylglycinol auxiliary was also developed. The stereochemical assignment of the homoallylic amine was

  将衍生自苯甘醇的手性醛亚胺在酒精溶剂中与铟粉/溴代烯丙基酯非对映选择性地烯丙基化。脂族和芳族醛亚胺都提供了具有高非对映选择性的所需产物的良好产率。还开发了用于消去苯基甘醇辅助剂的无消旋方案。通过NMR光谱对均烯丙基胺进行立体化学分配，并提出了过渡态模型来解释选择性。
• Nickel-Catalyzed Allylation of α-Amido Sulfones To Form Protected Homoallylic Amines
  作者：Daniel Weix、Jill Caputo、Marina Naodovic

  DOI：10.1055/s-0034-1379539

  日期：——

  The allylation of stable, protected imine precursors, α-amido sulfones, with allylic acetates to form homoallylic amines is catalyzed by nickel under mild reducing conditions. Aliphatic and aryl imines are tolerated, as are substituted allylic acetates. In the case of substituted allylic acetates, high diastereoselectivity and regioselectivity is observed in some cases and the branched product is obtained

  稳定的、受保护的亚胺前体α-酰氨基砜与烯丙基乙酸酯烯丙基化形成均烯丙基胺是在温和的还原条件下由镍催化的。脂肪族亚胺和芳基亚胺以及取代的醋酸烯丙酯都可以耐受。在取代的乙酸烯丙酯的情况下，在某些情况下观察到高的非对映选择性和区域选择性，并且几乎只获得支化产物。
• Pd(II)-Catalyzed Allylic C–H Amination for the Preparation of 1,2- and 1,3-Cyclic Ureas
  作者：Yasuhiro Nishikawa、Seikou Kimura、Yuri Kato、Natsuka Yamazaki、Osamu Hara

  DOI：10.1021/ol5037453

  日期：2015.2.20

  A general synthesis of 1,2- and 1,3-cyclic ureas is accomplished by intramolecular allylic C-H amination employing Pd(TFA)(2)/bis-sulfoxide as a catalyst. By careful modification of substrates and catalyst, a variety of 1,2-cyclic ureas are accessible from not previously employed terminal olefins substituted in allylic or vinylic positions. Furthermore, MS4A is found to be an effective additive for the synthesis of 1,3-cyclic ureas in good yields and excellent diastereoselectivities.
• <i>N</i>-Boc Amines to Oxazolidinones via Pd(II)/Bis-sulfoxide/Brønsted Acid Co-Catalyzed Allylic C–H Oxidation
  作者：Thomas J. Osberger、M. Christina White

  DOI：10.1021/ja506036q

  日期：2014.8.6

  A Pd(II)/bis-sulfoxide/Bronsted acid catalyzed allylic C-H oxidation reaction for the synthesis of oxazolidinones from simple N-Boc amines is reported. A range of oxazolidinones are furnished in good yields (avg 63%) and excellent diastereoselectivities (avg 15:1) to furnish products regioisomeric from those previously obtained using allylic C-H amination reactions. Mechanistic studies suggest the role of the phosphoric acid is to furnish a Pd(II)bis-sulfoxide phosphate catalyst that promotes allylic C-H cleavage and pi-allylPd functionalization with a weak, aprotic oxygen nucleophile and to assist in catalyst regeneration.