(3aR,8aR)-6-t-butyl-2,2-dimethyl-4,4,8,8-tetra(naphthalen-2-yl)tetrahydro[1,3]dioxolo[4,5-e]-[1,3,2]dioxaphosphepine | 1227475-33-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (3aR,8aR)-6-t-butyl-2,2-dimethyl-4,4,8,8-tetra(naphthalen-2-yl)tetrahydro[1,3]dioxolo[4,5-e]-[1,3,2]dioxaphosphepine
• 英文别名: (1R,7R)-4-tert-butyl-9,9-dimethyl-2,2,6,6-tetra(naphthalen-2-yl)-3,5,8,10-tetraoxa-4-phosphabicyclo[5.3.0]decane；(3aR,8aR)-6-tert-butyl-2,2-dimethyl-4,4,8,8-tetranaphthalen-2-yl-3a,8a-dihydro-[1,3]dioxolo[4,5-e][1,3,2]dioxaphosphepine
• CAS: 1227475-33-3
• 化学式: C₅₁H₄₅O₄P
• 分子量: 752.89
• InChiKey: JYXUIRIXLKQHOK-NZCKGYRVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.1
• 重原子数：
  56
• 可旋转键数：
  5
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  叔丁基锂 、 (3aR,8aR)-6-Chloro-2,2-dimethyl-4,4,8,8-tetra-naphthalen-2-yl-tetrahydro-[1,3]dioxolo[4,5-e][1,3,2]dioxaphosphepine 以 四氢呋喃 、 正戊烷 为溶剂， 以2.22 g的产率得到(3aR,8aR)-6-t-butyl-2,2-dimethyl-4,4,8,8-tetra(naphthalen-2-yl)tetrahydro[1,3]dioxolo[4,5-e]-[1,3,2]dioxaphosphepine
  参考文献：
  名称：

  Expeditious synthesis of TADDOL-derived phosphoramidite and phosphonite ligands

  摘要：

  A simple and reliable protocol for the synthesis of TADDOL-derived monodentate ligands is reported. The reaction of the requisite TADDOL with PCl3 is immediately followed by the treatment of the crude intermediate with both nitrogen and carbon nucleophiles. Several previously unknown or difficult-to-make phosphoramidite and phosphonite ligands L1-L3 and L4-L9 were accessed using this novel procedure. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2010.03.010
• 作为试剂：
  描述：

  二甲基苯基硅烷 、 1-苯基-2-(丙-2-亚基氨基)氧基乙醇 在 (3aR,8aR)-6-t-butyl-2,2-dimethyl-4,4,8,8-tetra(naphthalen-2-yl)tetrahydro[1,3]dioxolo[4,5-e]-[1,3,2]dioxaphosphepine 、 copper(l) chloride 、 sodium t-butanolate 作用下， 以 甲苯 为溶剂， 反应 40.0h， 以66%的产率得到(R)-propan-2-one-O-(2-dimethylphenylsilyloxy-2-phenylethyl)oxime
  参考文献：
  名称：

  肟醚官能化醇的催化对映选择性脱氢Si-O偶联

  摘要：

  醇的不对称甲硅烷基化是解决其动力学拆分的一种不寻常但有效的方法，并且Cu-H催化的脱氢Si-O偶联特别值得注意，因为形成了二氢作为唯一的副产物。我们的实验室以前曾报道过对嗪供体官能化的醇进行非对映选择性（与硅-立体异构硅烷反应）和对映选择性（与非手性硅烷）Si-O偶联反应。这种局限性，即需要氮供体原子，促使我们寻求同样有用的供体基团。肟醚被确定为合适的替代物，并且我们在本文中描述了一系列肟醚官能化的醇的制备。为了评估其动力学分辨率中的不同取代模式，这些在使用硅固相硅烷的试剂控制的Si-O偶联中进行了测试。

  DOI：

  10.1016/j.tet.2011.06.102

文献信息

• Catalytic Asymmetric SiO Coupling of Simple Achiral Silanes and Chiral Donor-Functionalized Alcohols
  作者：Andreas Weickgenannt、Marius Mewald、Thomas W. T. Muesmann、Martin Oestreich

  DOI：10.1002/anie.200905561

  日期：2010.3.15

  Silicon alley: SiH and HOR are enantioselectively coupled in the presence of a chiral CuH complex. In this way, the kinetic resolution of racemic mixtures of alcohols is accomplished through asymmetric protection with standard silanes (see scheme; R=aryl or alkyl, Ar=3,5‐xylyl, Np=2‐naphthyl; s=selectivity factor).

  硅胡同：硅 H和H 或者，对映选择性地耦合在手性铜的存在 H络合物。通过这种方式，醇的外消旋混合物的动力学拆分可通过使用标准硅烷进行不对称保护来实现（参见方案; R =芳基或烷基，Ar = 3,5-二甲苯基，Np = 2-萘基; s =选择性因子）。
• Expeditious synthesis of TADDOL-derived phosphoramidite and phosphonite ligands
  作者：Marius Mewald、Andreas Weickgenannt、Roland Fröhlich、Martin Oestreich

  DOI：10.1016/j.tetasy.2010.03.010

  日期：2010.5

  A simple and reliable protocol for the synthesis of TADDOL-derived monodentate ligands is reported. The reaction of the requisite TADDOL with PCl3 is immediately followed by the treatment of the crude intermediate with both nitrogen and carbon nucleophiles. Several previously unknown or difficult-to-make phosphoramidite and phosphonite ligands L1-L3 and L4-L9 were accessed using this novel procedure. (C) 2010 Elsevier Ltd. All rights reserved.