N-[(3aR,7aR)-1,3-dibenzyl-2-oxido-3a,4,5,6,7,7a-hexahydrobenzo[d][1,3,2]diazaphosphol-2-ium-2-yl]-1-phenylmethanimine | 1013026-17-9

• 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-[(3aR,7aR)-1,3-dibenzyl-2-oxido-3a,4,5,6,7,7a-hexahydrobenzo[d][1,3,2]diazaphosphol-2-ium-2-yl]-1-phenylmethanimine
• CAS: 1013026-17-9
• 化学式: C₂₇H₃₀N₃OP
• 分子量: 443.528
• InChiKey: BYORFQKTJOUZNH-KAYWLYCHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  32
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  41.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  二苯亚甲基甘氨酸乙酯 、 N-[(3aR,7aR)-1,3-dibenzyl-2-oxido-3a,4,5,6,7,7a-hexahydrobenzo[d][1,3,2]diazaphosphol-2-ium-2-yl]-1-phenylmethanimine 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 生成 ethyl (2S,3S)-3-(((3aR,7aR)-1,3-dibenzyl-2-oxidooctahydrobenzo[d][1,3,2]diazaphosphol-2-yl)amino)-2-((diphenylmethylene)amino)-3-phenylpropanoate 、
  参考文献：
  名称：

  Chiral N-phosphonyl imine chemistry: Asymmetric synthesis of α,β-diamino esters by reacting phosphonyl imines with glycine enolates

  摘要：

  Chiral phosphonyl imines attached with N-isopropyl protection group were found to react with lithium glycine enolates under convenient conditions to give alpha,beta-diamino esters. Thirteen examples have been examined in good to excellent chemical yields (85-97%) diastereoselectivity (up to 99% de). By treating with HBr at room temperature, the chiral auxiliary can be readily removed and recycled. The absolute structure has been unambiguously determined by converting a product to a known sample. Published by Elsevier Ltd.

  DOI：

  10.1016/j.bmcl.2009.03.001

文献信息

• Chiral N-phosphonyl imine chemistry: an efficient asymmetric synthesis of chiral N-phosphonyl propargylamines
  作者：Parminder Kaur、Gaurav Shakya、Hao Sun、Yi Pan、Guigen Li

  DOI：10.1039/b923914f

  日期：——

  A variety of substituted chiral propargylamines have been synthesized by reacting chiral N-phosphonylimines with lithium aryl/alkyl acetylides. Seventeen examples were studied to give excellent yields (>90%) and diastereoselectivities (96 : 4 to 99 : 1). It was found that the types of bases for generating acetylides and solvents are crucial for effectiveness of this asymmetric reaction. In addition, N,N-isopropyl group on chiral N-phosphonylimine auxiliary was proven to be superior to other protecting groups in controlling diastereoselectivity.

  通过手性 N-膦酰亚胺与芳基/烷基乙酰化锂反应，合成了多种取代的手性丙炔胺。对 17 个实例进行了研究，结果表明它们具有极高的产率（大于 90%）和非对映选择性（96:4 至 99:1）。研究发现，生成乙酰化物的碱和溶剂类型对这一不对称反应的有效性至关重要。此外，在控制非对映选择性方面，手性 N-膦酰亚胺辅助剂上的 N,N-异丙基被证明优于其他保护基团。
• Research Article: Asymmetric Hydrophosphylation of Chiral N-Phosphonyl Imines Provides an Efficient Approach to Chiral α-Amino Phosphonates
  作者：Parminder Kaur、Walter Wever、Trideep Rajale、Guigen Li

  DOI：10.1111/j.1747-0285.2010.01013.x

  日期：2010.10

  Chiral N‐phosphonylimines were found to react with lithium phosphites to provide various substituted chiral α‐amino phosphonates in excellent yields (94–97%) and diastereoselectivities (93:7–99:1). The types of bases utilized for generating the nucleophile are crucial for the effectiveness of asymmetric induction. In addition, N,N‐isopropyl group on chiral N‐phosphonylimine auxilliary was proven to be superior to other protecting groups in controlling diastereoselectivity. The absolute configuration was unambiguously determined by converting a chiral α‐amino phosphonate into its authentic N‐Cbz derivative.
• Asymmetric Synthesis of α-Amino-1,3-dithianes via Chiral <i>N</i>-Phosphonyl Imine-Based Umpolung Reaction Without Using Chromatography and Recrystallization
  作者：Padmanabha V. Kattamuri、Teng Ai、Suresh Pindi、Yinwei Sun、Peng Gu、Min Shi、Guigen Li

  DOI：10.1021/jo200070d

  日期：2011.4.15

  A series of alpha-amino-1,3-dithianes have been synthesized via the asymmetric Umpolung reaction of 2-lithio-1,3-dithianes with chiral N-phosphonyl imines in good chemical yields (up to 82%) and good to excellent diastereoselectivities (>99:1). The manner by which chiral N-phosphonyl imines are slowly added into the solution of 2-lithio-1,3-dithiane was found to be crucial for achieving excellent diastereoselectivity. The current synthesis was proven to follow the GAP chemistry (group-assistant-purification chemistry) process, which avoids traditional purification techniques of chromatography or recrystallization, i.e., the pure chiral alpha-amino-1,3-dithianes attached with the chiral N-phosphonyl group were readily obtained by washing the solid crude products with hexane or a mixture of hexane ethyl acetate.
• Chiral N-phosphonyl imine chemistry: Asymmetric synthesis of α,β-diamino esters by reacting phosphonyl imines with glycine enolates
  作者：Teng Ai、Guigen Li

  DOI：10.1016/j.bmcl.2009.03.001

  日期：2009.7

  Chiral phosphonyl imines attached with N-isopropyl protection group were found to react with lithium glycine enolates under convenient conditions to give alpha,beta-diamino esters. Thirteen examples have been examined in good to excellent chemical yields (85-97%) diastereoselectivity (up to 99% de). By treating with HBr at room temperature, the chiral auxiliary can be readily removed and recycled. The absolute structure has been unambiguously determined by converting a product to a known sample. Published by Elsevier Ltd.