(3aR,7aR)-1,3-dibenzyl-2-hydroxy-2-imino-3a,4,5,6,7,7a-hexahydrobenzo[d][1,3,2]diazaphosphole | 1013026-13-5

• 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: (3aR,7aR)-1,3-dibenzyl-2-hydroxy-2-imino-3a,4,5,6,7,7a-hexahydrobenzo[d][1,3,2]diazaphosphole
• CAS: 1013026-13-5
• 化学式: C₂₀H₂₆N₃OP
• 分子量: 355.42
• InChiKey: YRYXBKPHIGONGQ-WOJBJXKFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  49.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-苄氧基苯甲醛 、 (3aR,7aR)-1,3-dibenzyl-2-hydroxy-2-imino-3a,4,5,6,7,7a-hexahydrobenzo[d][1,3,2]diazaphosphole 在 四氯化钛 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以65%的产率得到(3aR,7aR)-1,3-dibenzyl-2-(((E)-4-(benzyloxy)benzylidene)amino)octahydrobenzo[d][1,3,2]diazaphosphole 2-oxide
  参考文献：
  名称：

  Chiral N-phosphonyl imine chemistry: new reagents and their applications for asymmetric reactions

  摘要：

  Novel chiral N-phosphonyl imines 2 have been designed and synthesized using chiral N-phosphoramide 1. These N-phosphonyl imines have been successfully utilized for asymmetric aza-Darzens reaction and asymmetric aza-Henry reaction. The C(2)-symmetric chiral auxiliary tolerates oxidation, is not sensitive to racemization and can be recycled for large scale synthesis. (c) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2008.01.028

文献信息

• Chiral phosphoramides, chiral N-phosphonimines and methods for forming the same
  申请人：Sun Xiangzhen

  公开号：US20100160681A1

  公开（公告）日：2010-06-24

  This application relates to the design and synthesis of new chiral imines reagents which can be utilized for the synthesis of chiral drugs and their precursors. It describes the design of the free NH2-group-attached chiral phosphoramides, a chiral N-phosphonimines and the methods for forming the same. The free NH2-group-attached chiral phosphoramides, having the structure of formula (I): wherein R1 and R2 are independently any organic groups. The synthesis of N-phosphoramides was performed starting from chiral 1,2-diamines via the following steps: N,N′-dialkylation consisting of aldehyde condensation and reduction, cyclization with phosphoryl halide, substitution of halide with azide anion and hydrogenation of azides. The N-phosphonyl imines are synthesized by condensation of N-phosphoramides with aldehydes. Quantitative yield was obtained for each of the four steps without special purification. All precursors were obtained as white solids. It should be addressed that after each application reaction of N-phosphonyl imines, N,N′-dialkyl vicinal diamine auxiliaries can be recovered quantitatively with one-time extraction using n-butanol and re-used.

  该应用涉及新手性亚胺试剂的设计和合成，可用于合成手性药物及其前体。它描述了自由NH2基固定的手性磷酰胺、手性N-膦酰亚胺的设计以及其制备方法。自由NH2基固定的手性磷酰胺的结构式如下：其中R1和R2是任意的有机基团。N-磷酰胺的合成是从手性1,2-二胺开始进行的，经过以下步骤：醛缩和还原的N,N'-二烷基化，磷酰卤素的环化，卤素的取代反应和氮化物的氢化反应。N-膦酰亚胺是通过N-磷酰胺与醛的缩合反应合成的。每个步骤都可以获得定量收率，无需特殊纯化。所有前体均为白色固体。需要指出的是，在每次应用N-膦酰亚胺反应后，N,N'-二烷基邻二胺辅助剂可以使用正丁醇一次性萃取并再次使用。
• [EN] CHIRAL PHOSPHORAMIDES, CHIRAL N-PHOSPHONIMINES AND METHODS FOR FORMING THE SAME<br/>[FR] PHOSPHORAMIDES CHIRAUX, N-PHOSPHONIMINES CHIRALES ET PROCÉDÉS POUR LEUR PRÉPARATION
  申请人：NOWA PHARMACEUTICALS CO LTD

  公开号：WO2009000202A1

  公开（公告）日：2008-12-31

  [EN] The invention relates free NH2-group-attached chiral phosphoramides, a chiral N-phosphonimines and the methods for forming the same. The free NH2-group-attached chiral phosphoramides, having the structure of formula (I) wherein R1 and R2 are independently any organic groups.
  [FR] L'invention concerne des phosphoramides chiraux sur lesquels est attaché un groupe NH2 libre, des N-phosphonimines chirales, et des procédés pour leur préparation. Les phosphoramides chiraux sur lesquels est attaché un groupe NH2 libre, ont la structure de formule (I) dans laquelle R1 et R2 sont indépendamment n'importe quel groupe organique.
• Chiral N-phosphonyl imine chemistry: new reagents and their applications for asymmetric reactions
  作者：Adiseshu Kattuboina、Guigen Li

  DOI：10.1016/j.tetlet.2008.01.028

  日期：2008.3

  Novel chiral N-phosphonyl imines 2 have been designed and synthesized using chiral N-phosphoramide 1. These N-phosphonyl imines have been successfully utilized for asymmetric aza-Darzens reaction and asymmetric aza-Henry reaction. The C(2)-symmetric chiral auxiliary tolerates oxidation, is not sensitive to racemization and can be recycled for large scale synthesis. (c) 2008 Elsevier Ltd. All rights reserved.