(4R,5R)-2-Chloro-1,3-dimethyl-4,5-diphenyl-[1,3,2]diazaphospholidine 2-oxide | 137943-78-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: (4R,5R)-2-Chloro-1,3-dimethyl-4,5-diphenyl-[1,3,2]diazaphospholidine 2-oxide
• 英文别名: (4R,5R)-2-chloro-1,3-dimethyl-4,5-diphenyl-1,3,2λ5-diazaphospholidine 2-oxide
• CAS: 137943-78-3
• 化学式: C₁₆H₁₈ClN₂OP
• 分子量: 320.758
• InChiKey: FQRUXSPLEVYWRU-HZPDHXFCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.69
• 重原子数：
  21.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  23.55
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  3-甲基-2-丁醇 、 (4R,5R)-2-Chloro-1,3-dimethyl-4,5-diphenyl-[1,3,2]diazaphospholidine 2-oxide 在 sodium hydride 作用下， 生成 (4R,5R)-2-(1,2-Dimethyl-propoxy)-1,3-dimethyl-4,5-diphenyl-[1,3,2]diazaphospholidine 2-oxide
  参考文献：
  名称：

  A new reagent for the determination of the optical purity of primary, secondary, and tertiary chiral alcohols and of thiols

  摘要：

  A new reagent is described for the determination of the enantiomeric excess of chiral alcohols. This derivatizing agent (22) is a diazaphospholidine, easily prepared from hexamethylphosphorous triamide (HMPT) and a chiral diamine having a C2 axis of symmetry: (R,R)-N,N'-dimethylcyclohexane-1,2-diamine. A large array of primary, secondary, and tertiary alcohols, functionalized or not, as well as thiols were successfully tested. The derivatization is fast at room temperature, proceeds without kinetic discrimination, does not need any added cosolvent or coreagent, and may be run directly in an NMR tube. This new reagent allows an accurate analysis by P-31 NMR spectroscopy, and after conversion of the trivalent phosphorus derivative to the corresponding P-sulfide in the NMR tube, a new P-31 NMR spectrum may be recorded. In addition, most of the P-sulfide derivatives when submitted to GC or HPLC analyses exhibit base line separation.

  DOI：

  10.1021/jo00030a034
• 作为产物：
  描述：

  (1R,2R)-(+)-N,N-二甲基-1,2-二苯基-1,2-二乙胺 在 三乙胺 、 三氯氧磷 作用下， 以 甲苯 为溶剂， 以94%的产率得到(4R,5R)-2-Chloro-1,3-dimethyl-4,5-diphenyl-[1,3,2]diazaphospholidine 2-oxide
  参考文献：
  名称：

  钴介导的手性氧化膦取代的线性烯二炔的[2 + 2 + 2]环加成中的高立体选择性诱导

  摘要：

  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。

  DOI：

  10.1016/s0040-4039(99)01137-5

文献信息

• Chiral Phosphoramide-Catalyzed Enantioselective Addition of Allylic Trichlorosilanes to Aldehydes. Preparative Studies with Bidentate Phosphorus-Based Amides
  作者：Scott E. Denmark、Jiping Fu、Michael J. Lawler

  DOI：10.1021/jo052203h

  日期：2006.2.1

  that more than one Lewis basic moiety (phosphoramide) is involved in the rate- and stereochemistry-determining step of enantioselective allylation, bidentate chiral phosphoramides were developed. Different chiral phosphoramide moieties were connected by tethers of methylene chains of varying length. The rate and enantioselectivity of allylation with allyltrichlorosilane promoted by the bidentate phosphoramides

  基于机械学的见解，即对映选择性烯丙基化的速率和立体化学决定步骤涉及多个路易斯基本部分（磷酰胺），开发了二齿手性磷酰胺。通过不同长度的亚甲基链的束缚连接不同的手性磷酰胺部分。发现由二齿磷酰胺促进的与烯丙基三氯硅烷的烯丙基化的速率和对映选择性高度依赖于系链长度。设计了一种新的基于2,2'-双吡咯烷骨架的磷酰胺，在烯丙基化反应中具有良好的收率，有效的转化率和高的对映选择性。对映体纯的2,2'-双吡咯烷的合成很容易通过吡咯烷的光二聚化，然后用四氢呋喃进行拆分而大规模完成。l（或d）酒石酸。用各种取代的烯丙基三氯硅烷和不饱和醛检查了烯丙基化反应的范围。通过添加不对称的γ-二取代的烯丙基三氯硅烷，该方法已应用于立体异构的季中心的构建。
• A new reagent for a very simple and efficient determination of enantiomeric purity of alcohols by 31P NMR
  作者：Alexandre Alexakis、Stephane Mutti、Jean F. Normant、Pierre Mangeney

  DOI：10.1016/s0957-4166(00)86347-8

  日期：1990.1

  A new reagent is described for the determination of enantiomeric excess of chiral alcohols. This derivatizing agent allows an accurate analysis by 31P NMR. A large array of primary, secondary, and tertiary alcohols, functionalized or not, were successfully tested. Reagent 7 is easy to prepare and reacts alone with the chiral alcohol, at room temperature, eventually directly in the NMR tube.

  描述了一种用于测定手性醇对映体过量的新试剂。该衍生剂可以通过31 P NMR进行准确的分析。成功地测试了各种伯醇，仲醇和叔醇，无论它们是否官能化。试剂7易于制备，可与手性醇在室温下单独反应，最终直接在NMR管中进行反应。
• 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，