2-chloro-2,3,3a,4,5,6,7,7a-octahydro-1,3-bis(phenylmethyl)-1H-1,3,2-benzodiazaphosphole-2-oxide | 368887-07-4

• 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: 2-chloro-2,3,3a,4,5,6,7,7a-octahydro-1,3-bis(phenylmethyl)-1H-1,3,2-benzodiazaphosphole-2-oxide
• 英文别名: (3aR,7aR)-1,3-dibenzyl-2-chloro-3a,4,5,6,7,7a-hexahydrobenzo[d][1,3,2]diazaphosphole 2-oxide
• CAS: 368887-07-4
• 化学式: C₂₀H₂₄ClN₂OP
• 分子量: 374.85
• InChiKey: UGLRRFZQTGNVTR-WOJBJXKFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 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：
  23.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-chloro-2,3,3a,4,5,6,7,7a-octahydro-1,3-bis(phenylmethyl)-1H-1,3,2-benzodiazaphosphole-2-oxide 在 正丁基锂 、 三乙胺 作用下， 以 甲苯 为溶剂， 反应 13.0h， 生成 Bis-((3aR,7aR)-1,3-dibenzyl-2-oxo-octahydro-2λ⁵-benzo[1,3,2]diazaphosphol-2-yl)-phenyl-amine
  参考文献：
  名称：

  A simple protocol for the synthesis of chiral bidentate imidodiphosphoric tetramide ligands: application in the metal-free asymmetric allylation of aldehydes

  摘要：

  The reaction of a series of chiral phosphorus triamides with BuLi and subsequent addition of a phosphoroxychloride diamide afforded the corresponding imidodiphosphoric tetramides in high yield. The use of enantiomerically pure diamides allowed access to bidentate imidodiphosphoric tetramides without loss of optical purity. These bidentate ligands have been used successfully to catalyze the addition of allyltrichlorosilane to aldehydes in an enantioselective fashion up to 60% ee. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)01047-4
• 作为产物：
  描述：

  (3aR,7aR)-Octahydro-1,3-dibenzyl-1,3,2-benzodiazaphosphole 2-oxide 在 四氯化锡 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 23.0h， 以30%的产率得到2-chloro-2,3,3a,4,5,6,7,7a-octahydro-1,3-bis(phenylmethyl)-1H-1,3,2-benzodiazaphosphole-2-oxide
  参考文献：
  名称：

  Koeller, Kevin J.; Rath, Nigam P.; Spilling, Christopher D., Phosphorus, Sulfur and Silicon and the Related Elements, 1995, vol. 103, # 1-4, p. 171 - 182

  摘要：

  DOI：

文献信息

• Cobalt(II)-Catalyzed Stereoselective Olefin Isomerization: Facile Access to Acyclic Trisubstituted Alkenes
  作者：Sheng Zhang、Deepika Bedi、Lu Cheng、Daniel K. Unruh、Guigen Li、Michael Findlater

  DOI：10.1021/jacs.0c02101

  日期：2020.5.13

  Stereoselective synthesis of trisubstituted alkenes is a long-standing challenge in organic chemistry, due to the small energy differences between E and Z isomers of trisubstituted alkenes (compared with 1,2-disubstituted alkenes). Transition metal-catalyzed isomerization of 1,1-disubstituted alkene can serve as an alternative approach to trisubsti-tuted alkenes, but it remains underdeveloped owing

  三取代烯烃的立体选择性合成是有机化学中长期存在的挑战，因为三取代烯烃的 E 和 Z 异构体之间的能量差异很小（与 1,2-二取代烯烃相比）。1,1-二取代烯烃的过渡金属催化异构化可以作为三取代烯烃的替代方法，但由于与反应效率和立体选择性有关的问题，它仍然不发达。在这里，我们展示了一种新型钴催化剂可以克服这些挑战，为获得广泛的三取代烯烃提供有效和立体选择性的途径。该协议与单烯和二烯兼容，并表现出良好的官能团耐受性和可扩展性。而且，它已被证明是构建有机发光体和氘代三取代烯烃的有用工具。对该机制的初步研究表明，该反应涉及钴氢化物途径。该反应的高立体选择性归因于 π-π 堆积效应和底物和催化剂之间的空间位阻。
• 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.
• Koeller, Kevin J.; Rath, Nigam P.; Spilling, Christopher D., Phosphorus, Sulfur and Silicon and the Related Elements, 1995, vol. 103, # 1-4, p. 171 - 182
  作者：Koeller, Kevin J.、Rath, Nigam P.、Spilling, Christopher D.

  DOI：——

  日期：——
• A simple protocol for the synthesis of chiral bidentate imidodiphosphoric tetramide ligands: application in the metal-free asymmetric allylation of aldehydes
  作者：Jasmin Hellwig、Thomas Belser、Jürgen F.K. Müller

  DOI：10.1016/s0040-4039(01)01047-4

  日期：2001.8

  The reaction of a series of chiral phosphorus triamides with BuLi and subsequent addition of a phosphoroxychloride diamide afforded the corresponding imidodiphosphoric tetramides in high yield. The use of enantiomerically pure diamides allowed access to bidentate imidodiphosphoric tetramides without loss of optical purity. These bidentate ligands have been used successfully to catalyze the addition of allyltrichlorosilane to aldehydes in an enantioselective fashion up to 60% ee. (C) 2001 Elsevier Science Ltd. All rights reserved.