(±)-tert-butyl (2-methylhex-5-en-3-yl)carbamate

• 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: (±)-tert-butyl (2-methylhex-5-en-3-yl)carbamate
• 英文别名: N-tert-butoxycarbonyl-1-(isopropyl)but-3-enamine；tert-butyl (2-methylhex-5-en-3-yl)carbamate；Tert-butyl (2-methylhex-5-en-3-yl)carbamate；tert-butyl N-(2-methylhex-5-en-3-yl)carbamate
• 化学式: C₁₂H₂₃NO₂
• 分子量: 213.32
• InChiKey: KULMJAKDQDSUPM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  (±)-tert-butyl (2-methylhex-5-en-3-yl)carbamate 在 正丁基锂 、 Pd(TFA)2/bis-sulfoxide 、 苯基-P-苯醌 作用下， 以 四氢呋喃 为溶剂， 反应 24.5h， 生成
  参考文献：
  名称：

  Pd(II)-Catalyzed Allylic C–H Amination for the Preparation of 1,2- and 1,3-Cyclic Ureas

  摘要：

  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.

  DOI：

  10.1021/ol5037453
• 作为产物：
  描述：

  2-异丙基-4-戊烯酸 、 二碳酸二叔丁酯 在 sodium azide 、 四丁基溴化铵 作用下， 以 四氢呋喃 为溶剂， 生成 (±)-tert-butyl (2-methylhex-5-en-3-yl)carbamate
  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

• Allylic CH Alkylation of Unactivated α-Olefins: Serial Ligand Catalysis Resumed
  作者：Andrew J. Young、M. Christina White

  DOI：10.1002/anie.201101654

  日期：2011.7.18

  A delicate interplay of several kinetically labile ligands is required for reactions that proceed through serial ligand catalysis mechanisms. An investigation of the disruption of this balance has enabled the development of a method for the intermolecular allylic CH alkylation of unactivated as well as activated α‐olefins (see example, Bn=benzyl).

  通过系列配体催化机制进行的反应需要几个动力学不稳定的配体之间的微妙相互作用。这种平衡的破坏的调查已使的方法的发展的分子间烯丙基Ç  H的未活化的烷基化以及活化的α烯烃（见实施例，BN =苄基）。
• 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。