(+)-N-{(1'S)-1-[(benzyloxy)methyl]prop-2-en-1-yl}-N-methoxybut-3-enamide | 1304540-32-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (+)-N-{(1'S)-1-[(benzyloxy)methyl]prop-2-en-1-yl}-N-methoxybut-3-enamide
• 英文别名: N-methoxy-N-[(2S)-1-phenylmethoxybut-3-en-2-yl]but-3-enamide
• CAS: 1304540-32-6
• 化学式: C₁₆H₂₁NO₃
• 分子量: 275.348
• InChiKey: XAWVCPRMEDXSRW-HNNXBMFYSA-N

物化性质

• 沸点：
  361.9±52.0 °C(predicted)
• 密度：
  1.051±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  20
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+)-N-{(1'S)-1-[(benzyloxy)methyl]prop-2-en-1-yl}-N-methoxybut-3-enamide 在 二异丁基氢化铝 作用下， 以96%的产率得到N-{(1S)-1-[(benzyloxy)methyl]prop-2-en-1-yl}-O-methylhydroxylamine
  参考文献：
  名称：

  Enantioselective Iridium-Catalyzed Allylic Substitutions with Hydroxamic Acid Derivatives as N-Nucleophiles

  摘要：

  Enantioselective Ir-catalyzed allylic aminations with hydroxamic acid derivatives are described. Catalysts were prepared in situ from [Ir(cod)Cl](2) or [Ir(dbcot)Cl](2), a phosphoramidite and base. In addition, pure (pi-allyl)Ir complexes containing cod or dbcot as auxiliary ligands were used. Very high degrees of regio- and enantioselectivity were achieved. The reaction products were transformed Into piperidine derivatives suited as precursors for aza-sugars.

  DOI：

  10.1021/ol200688d
• 作为产物：
  描述：

  (E)-4-benzyloxy-2-butenyl methyl carbonate 在 4-二甲氨基吡啶 、 [{Ir(dibenzo[a,e]cyclooctatetraene)Cl}2] 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 N,N'-二环己基碳二亚胺 、 三氟乙酸 、 (3,5-dioxa-4-phospha-cyclohepta[2,1-a;3,4-a']dinaphthalen-4-yl)-bis-(1-phenyl-ethyl)-amine 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 4.5h， 生成 (+)-N-{(1'S)-1-[(benzyloxy)methyl]prop-2-en-1-yl}-N-methoxybut-3-enamide
  参考文献：
  名称：

  Enantioselective Iridium-Catalyzed Allylic Substitutions with Hydroxamic Acid Derivatives as N-Nucleophiles

  摘要：

  Enantioselective Ir-catalyzed allylic aminations with hydroxamic acid derivatives are described. Catalysts were prepared in situ from [Ir(cod)Cl](2) or [Ir(dbcot)Cl](2), a phosphoramidite and base. In addition, pure (pi-allyl)Ir complexes containing cod or dbcot as auxiliary ligands were used. Very high degrees of regio- and enantioselectivity were achieved. The reaction products were transformed Into piperidine derivatives suited as precursors for aza-sugars.

  DOI：

  10.1021/ol200688d

文献信息

• Addition of Organometallic Reagents to Chiral<i>N</i>‐Methoxylactams: Enantioselective Syntheses of Pyrrolidines and Piperidines
  作者：Mascha Jäkel、Jianping Qu、Tobias Schnitzer、Günter Helmchen

  DOI：10.1002/chem.201302735

  日期：2013.12.2

  Enantioselective iridium‐catalyzed allylic substitutions were used to prepare N‐allyl hydroxamic acid derivatives that were suitable for ring‐closing metathesis, giving N‐methoxylactams. Reactions of these derivatives with Grignard or organolithium compounds gave hemiaminals, which could be reduced diastereoselectively via acyliminium intermediates to give cis‐piperidines or cis‐pyrrolidines with substituents

  用对映选择性的铱催化的烯丙基取代基制备适合于闭环易位的N-烯丙基异羟肟酸衍生物，得到N-甲氧基内酰胺。这些衍生物与格氏试剂或有机锂化合物的反应，得到hemiaminals，其可非对映选择性经由acyliminium中间体，得到降低顺-哌啶或顺-pyrrolidines与取代基在2,6-或2,5-位置处分别。此外，可以通过与氰化钾/ AcOH进行相应反应来合成具有季碳中心的化合物。该程序应用于生物碱（-）-209D和（+）-脯氨酸的合成。