(2R,4S,5R)-2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidin-2-one | 54750-12-8

• 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: (2R,4S,5R)-2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidin-2-one
• 英文别名: (4S)-2-chloro-3,4r-dimethyl-5c-phenyl-[1,3,2]oxazaphospholidine 2t-oxide；(2R,4S,5R)-2-chloro-3,4-dimethyl-5-phenyl-1,3,2lambda5-oxazaphospholidine 2-oxide；(2R,4S,5R)-2-chloro-3,4-dimethyl-5-phenyl-1,3,2λ5-oxazaphospholidine 2-oxide
• CAS: 54750-12-8
• 化学式: C₁₀H₁₃ClNO₂P
• 分子量: 245.645
• InChiKey: OXYULDFETWMUMU-KPCOEVGBSA-N

物化性质

• 沸点：
  320.2±45.0 °C(Predicted)
• 密度：
  1.30±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2R,4S,5R)-2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidin-2-one 在 盐酸肼 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以90%的产率得到(2S,4S,5R)-3,4-dimethyl-2-hydrazino-5-phenyl-1,3,2-oxazaphospholidin-2-one
  参考文献：
  名称：

  Preparation of Chiral Phosphorus(V) Reagents and Their Uses with Borane in the Enantioselective Reduction of Ketones

  摘要：

  AbstractChiral pentavalent phosphorus reagents 5–17 were prepared from POCl3 and ephedrine (or the related α‐amino alcohols), followed by substitution with nucleophiles of phenylmagnesium bromide, alcohols, amines, diamines and triamines. The substitution reactions occurred in a stereospecific manner with retention of the configuration at the phosphorus center. The structures of these phosphorus(V) reagents were determined by spectral methods and verified by X‐ray diffraction in several instances. These phosphorus(V) reagents were used with borane/dimethylsulfide complex in the enantioselective reduction of aromatic, aliphatic and heterocyclic ketones. The phosphorus(V) reagents likely functioned as Lewis bases to react with borane, forming in situ zwitterionic species as the chiral reducing agents. The reactions were generally carried out at 0 °C in tetrahydrofuran solution with a molar ratio of ketone/borane/phosphoramidate = 1:1:0.2 to afford secondary alcohols with modest enantioselectivity, up to 67% ee in the reduction of 4′‐methylacetophenone.

  DOI：

  10.1002/jccs.199900108
• 作为产物：
  描述：

  麻黄碱 在 三氯氧磷 作用下， 以60%的产率得到(2R,4S,5R)-2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidin-2-one
  参考文献：
  名称：

  用磷 31 核磁共振技术测定醇和胺的对映体纯度

  摘要：

  利用dusulfure-2 de la chloro-2 dimethyl-3,4 phenyl-5 oxazaphospholidine-1,3,2 commereactif de derivatiisation

  DOI：

  10.1021/ja00329a072

文献信息

• Highly stereoselective induction in the cobalt-mediated [2+2+2] cycloaddition of chiral phosphine oxides substituted linear enediynes
  作者：Franck Slowinski、Corinne Aubert、Max Malacria

  DOI：10.1016/s0040-4039(99)01137-5

  日期：1999.8

  The cobalt(I)-catalyzed highly stereoselective [2+2+2] cyclization has been realized for the first time with chiral phosphine oxides substituted linear enediynes. Depending the substituents on the phosphorus atom, the cycloaddition was achieved with a level of diastereoselectivity of 74%.

  钴（I）催化的高度立体选择性[2 + 2 + 2]环化反应是首次用手性氧化膦取代的线性二烯炔来实现的。取决于磷原子上的取代基，以74％的非对映选择性水平实现环加成。
• Diastereoselective Cobalt-Mediated [2 + 2 + 2] Cycloadditions of Substituted Linear Enediynes Phosphine Oxides:  Scope and Limitations
  作者：Franck Slowinski、Corinne Aubert、Max Malacria

  DOI：10.1021/jo026212r

  日期：2003.1.1

  Variously substituted linear enediynes phosphines oxides possessing the double bond at either the terminal or internal position and with the phosphine oxide appended onto the alkyne or the alkene terminus have been prepared. Their cobalt(I)-mediated cyclizations produce the eta(4)-complexed tricyclic compounds in high yields. The endo/exo selectivity depends on both the position of the phosphine oxide

  制备了在末端或内部位置均具有双键并且将氧化膦附接至炔烃或烯烃末端的各种取代的线性烯二炔膦氧化物。他们的钴（I）介导的环化以高收率生产出eta（4）络合的三环化合物。内/外选择性取决于烯二炔上氧化膦的位置和系链中双键的位置。对于手性氧化膦，观察到一定程度的诱导，并且取决于磷原子上的取代基，非对映选择性可以达到74％。迄今为止，这是报道的建立立体生成中心的环化反应的最高水平。关于我们所有的结果，
• Stereoselective synthesis of homochiral (E)-vinyl phosphonates derived from (-)-ephedrine
  作者：Thomas Taapken、Siegfried Blechert

  DOI：10.1016/00404-0399(50)1351-h

  日期：1995.9

  A new synthesis of homochiral vinyl phosphonates starting from 1-alkynes is described., The title compounds were obtained in good yields by the reaction of chiral 2-chloro-1,3,2-oxa2aphospholidin-2-one (1) with the “ate”-complexes of vinyl alanes., The latter were prepared by zirconocene dichloride catalyzed hydroalumination of 1-alkynes with diisobutyl aluminum hydride (DIBAH).

  描述了一种从1-炔烃开始合成的手性乙烯基膦酸酯的新合成方法。通过手性2-氯-1,3,2-氧杂2a磷酰化-2-（1）与“后者是通过二茂锆茂催化的1-炔烃与氢化二异丁基铝（DIBAH）的加氢铝化反应制备的。
• Monitoring site-specific natural hydrogen isotope fractionation using a novel phosphorus-containing chiral discriminating reagent
  作者：Gerhard Hägele、Bruno Boisnière、Isabelle Helie、Claude Rabiller、Gérard J. Martin、Maryvonne L. Martin

  DOI：10.1002/mrc.1260290812

  日期：1991.8

  31P NMR. Analysis of 1D and 2D NMR spectra and theoretical simulations enable the 1H and 13C chemical shifts of CA and CB to be determined. The chemical shift differences exhibited by the methylenic hydrogens of the ethoxy moiety in CA and CB are of the order of 0.3 ppm. These large differences can be mainly attributed to ring current effects. Such effects have been estimated using two different methods

  报道了一种新型手性鉴别试剂的合成，即 L-薄荷基苯基磷酰氯与乙醇反应生成的酯。该试剂 C 旨在区分乙醇的 R 和 S 单氘化对映异构体，它构成了天然产物机理研究和来源推断的重要同位素探针。组成试剂 C 的两个 P-差向异构结构 CA 和 CB 的比例可通过 31P NMR 直接获得。对 1D 和 2D NMR 光谱和理论模拟的分析能够确定 CA 和 CB 的 1H 和 13C 化学位移。CA 和 CB 中乙氧基部分的亚甲基氢表现出的化学位移差异约为 0.3 ppm。这些巨大的差异主要归因于环流效应。已经使用两种不同的方法基于两种差向异构体 CA 和 CB 的模型构象估计了这种效应，它们是从量子力学方法中的能量最小化推导出来的。无法从质子光谱中确定与 CA 和 CB 异构体中 pro-R 和 pro-S 位置相关的化学位移差异 δR(C)-δS(C) 的相对符号。环电流计算表明δR(C)-δ
• Stereoselective Umpolung Reactions with MetalatedP-Chiral Cyanohydrin Phosphates—Enantioselective Synthesis of Tertiary Cyanohydrins
  作者：Thomas Schrader

  DOI：10.1002/chem.19970030815

  日期：1997.8

  AbstractWe present the first cyanohydrin derivative4that allows diastereoselective umpolung reactions. In4the OH group of the cyanohydrin is linked with a chiral phosphate, which can be removed hydrolytically after asymmetric synthesis. Cyclization of pseudoephedrine1dwith POCl3gave2d. This was followed by addition of racemic benzaldehyde cyanohydrin3to give the key intermediate4dwith complete retention of the configuration at phosphorus. Deprotonation of4d, followed by addition of a wide variety of electrophiles afforded the crystalline products5with high diastereomeric excesses (deup to 94%). High asymmetric induction was also achieved for the reaction of4−Li+with acyl halides, α‐bromoacetates, 2‐cycloalkenones, α,β‐unsaturated esters, and γ‐bromoacetates. Lewis acid assisted hydrolysis proceeded without racemization and gave high yields of ketone cyanohydrins6. From the ring‐opened chiral auxiliary7, optically pure pseudoephedrine1was readily recovered by acid hydrolysis. Optically pure (R) and (S) ketone cyanohydrins are now accessible in a very general strategy, which circumvents the substrate limitations of enzymatic synthesis.