N-[(3aR,7aR)-1,3-bis(naphthalen-1-ylmethyl)-2-oxido-3a,4,5,6,7,7a-hexahydrobenzo[d][1,3,2]diazaphosphol-2-ium-2-yl]-1-phenylmethanimine | 1186139-45-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: N-[(3aR,7aR)-1,3-bis(naphthalen-1-ylmethyl)-2-oxido-3a,4,5,6,7,7a-hexahydrobenzo[d][1,3,2]diazaphosphol-2-ium-2-yl]-1-phenylmethanimine
• CAS: 1186139-45-6
• 化学式: C₃₅H₃₄N₃OP
• 分子量: 543.648
• InChiKey: ZKFBXXPGYJPSKK-VSJLXWSYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.1
• 重原子数：
  40
• 可旋转键数：
  6
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.23
• 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：

  、 N-[(3aR,7aR)-1,3-bis(naphthalen-1-ylmethyl)-2-oxido-3a,4,5,6,7,7a-hexahydrobenzo[d][1,3,2]diazaphosphol-2-ium-2-yl]-1-phenylmethanimine 在 potassium tert-butylate 作用下， 以 二氯甲烷 为溶剂， 反应 4.33h， 以79%的产率得到
  参考文献：
  名称：

  使用N-膦酰基亚胺和Ni（II）复杂的丙氨酸席夫碱通过基团辅助的纯化化学方法不对称合成手性α-甲基-α，β-二氨基酸衍生物

  摘要：

  报道了手性N-膦酰基亚胺与Ni（II）复合的丙氨酸席夫碱（Ala-Ni）之间的曼尼希反应。使用手性膦酰基助剂，可以简单地通过用助溶剂洗涤粗混合物来获得包含邻位手性中心，包括手性季碳中心的α-甲基-α，β-二氨基酸衍生物的单一异构体。对映体纯产物的绝对立体化学已经通过X射线晶体学分析明确确定。

  DOI：

  10.1021/acs.joc.6b01385

文献信息

• N,N-Diisopropyl-N-phosphonyl imines lead to efficient asymmetric synthesis of aziridine-2-carboxylic esters
  作者：Padmanabha V. Kattamuri、Yiwen Xiong、Yi Pan、Guigen Li

  DOI：10.1039/c3ob40251g

  日期：——

  Highly diastereoselective asymmetric synthesis of chiral aziridine-2-carboxylic esters is reported for 20 examples with good yields (51–87%) and excellent diastereoselectivities (>99 : 1 dr for most cases). The modified N-phosphonyl imines have proven to be superior to previous imine auxiliaries for the aza Darzens reaction by using a secondary isopropyl group to replace the primary benzyl group for

  据报道，手性氮丙啶-2-羧酸酯的高度非对映选择性不对称合成有 20 个实例，具有良好的产率（51-87%）和出色的非对映选择性（大多数情况下 >99:1 dr）。通过使用仲异丙基取代N , N的伯苄基，已证明改性N - 膦酰基亚胺在 aza Darzens 反应中优于以前的亚胺助剂。-二氨基保护。同时，发现在 4 Å 分子筛存在的情况下，在该温度下将预冷的亚胺溶液在 -78 °C 下缓慢加入到预先形成的 β-溴化烯醇锂混合物中的特殊操作对产率至关重要和非对映选择性。本方法可以提供对 β-羟基α-氨基酸和其他重要氨基构建块的简单和通用的访问。
• The GAP chemistry for chiral N-phosphonyl imine-based Strecker reaction
  作者：Parminder Kaur、Walter Wever、Suresh Pindi、Raizada Milles、Peng Gu、Min Shi、Guigen Li

  DOI：10.1039/c1gc15029d

  日期：——

  Chiral N-phosphonyl imines were found to be efficient electrophiles for reaction with diethylaluminium cyanide, a non-volatile and inexpensive cyanide source. The reaction produced chiral Strecker adducts, α-aminonitriles, in excellent chemical yields (94–98%) and diastereoselectivities (95 : 5 to >99%). This synthesis was confirmed to follow the GAP chemistry (group-assistant-purification chemistry) process, which can avoid traditional chromatography and recrystallization purifications, i.e., the pure chiral α-aminonitriles bearing a chiral N-phosphonyl group can be simply obtained by washing the solid crude products with hexane. The chiral N-phosphonyl auxiliary can be easily cleaved under mildly acidic conditions and quantitatively recycled by a one-time extraction with n-butanol.

  研究发现，手性 N-膦酰亚胺是与氰化二乙基铝（一种非挥发性的廉价氰化物来源）反应的高效亲电体。反应生成了手性 Strecker 加合物--α-氨基硝酰胺，化学收率（94-98%）和非对映选择性（95:5->99%）都非常好。经证实，该合成采用了 GAP 化学（基团辅助纯化化学）工艺，可避免传统的色谱法和重结晶纯化，即只需用正己烷洗涤固体粗产物，即可获得带有手性 N-膦酰基的纯手性 α-氨基硝酸酯。手性 N-膦酰基助剂可在弱酸性条件下轻松裂解，并通过正丁醇一次性萃取定量回收。
• 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。
• 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.
• 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.