2-N,N-diisopropylamino-1,3,2λ⁵-oxaselenaphospholane | 173203-50-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环化合物
• 英文名称: 2-N,N-diisopropylamino-1,3,2λ⁵-oxaselenaphospholane
• 英文别名: 2-(N,N-diisopropylamino)-1,3,2-oxaselenaphospholane；N,N-di(propan-2-yl)-1,3,2-oxaselenaphospholan-2-amine
• CAS: 173203-50-4
• 化学式: C₈H₁₈NOPSe
• 分子量: 254.171
• InChiKey: MNPQIEOLFPWPDE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.48
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-N,N-diisopropylamino-1,3,2λ⁵-oxaselenaphospholane 在 selenium 作用下， 以 苯 为溶剂， 以78%的产率得到2-N,N-diisopropylamino-1,3,2λ⁵-oxaselenaphospholane-2-selone
  参考文献：
  名称：

  The synthesis, X-ray and solid state NMR studies of 2-N,N-diisopropylamino-1,3,2λ5- oxaselenaphospholane-2-selone

  摘要：

  31P和77Se高分辨率固态核磁共振（NMR）光谱被用于研究2-N,N-二异丙基氨基-1,3,2Β5-氧杂硒杂磷杂环戊烷-2-硒酮的结构特性，该化合物是在开发用于核苷硫代磷酸酯立体控制合成的试剂的过程中合成的。31P CP/MAS和77Se CP/MAS实验均表明，不对称单元由两个围绕磷和硒中心具有不同几何形状的独立分子组成。31P化学位移张量的主要元素δii是通过使用WIN-MAS程序计算自旋边带强度得出的。已确定各向异性和不对称参数的值反映了磷环境的扭曲，并与X射线衍射数据非常吻合。从乙醚中生长出来的2-N,N-二异丙基氨基-1,3,2Β5-氧杂硒杂磷杂环戊烷-2-硒酮晶体是三斜晶系，空间群P，a=7.586(2)，b=13.003(1)，c=13.649(1)Å，α=89.683(8)°，β=75.42(1)°，γ=8.74(1)°，V=1285(6)Å

  DOI：

  10.1039/a606593g
• 作为产物：
  描述：

  2-hydroxyethyl selenol 、 dichloro-N,N-diisopropylaminophosphine 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以66%的产率得到2-N,N-diisopropylamino-1,3,2λ⁵-oxaselenaphospholane
  参考文献：
  名称：

  Diastereomers of Nucleoside 3'-O-(2-Thio-1,3,2-oxathia(selena)phospholanes): Building Blocks for Stereocontrolled Synthesis of Oligo(nucleoside phosphorothioate)s

  摘要：

  Diastereomerically pure 5'-O-DMT-nucleoside 3'-O-(2-thio-1,3,2-oxathiaphospholanes) (3) and their oxathiaphospholane ring-substituted analogues (20) were used for the synthesis of stereoregular oligo(nucleoside phosphorothioate)s (S-Oligos). The oxathiaphospholane ring-opening condensation requires the presence of strong organic base, preferably DBU. The yield of a single coupling step is ca. 95% and resulting S-Oligos are free of nucleobase- and sugar-phosphorothioate backbone modifications. The diastereomeric purity of products was estimated on the basis of diastereoselective degradation with Nuclease P1 and a mixture of snake venom phosphodiesterase and Serratia marcescens endonuclease. Thermal dissociation studies of heteroduplexes S-Oligos/DNA and S-Oligos/RNA showed that their stability is stereochemistry- and sequence-dependent.

  DOI：

  10.1021/ja00154a001

文献信息

• Diastereomers of Nucleoside 3'-O-(2-Thio-1,3,2-oxathia(selena)phospholanes): Building Blocks for Stereocontrolled Synthesis of Oligo(nucleoside phosphorothioate)s
  作者：Wojciech J. Stec、Andrzej Grajkowski、Anna Kobylanska、Boleslaw Karwowski、Maria Koziolkiewicz、Konrad Misiura、Andrzej Okruszek、Andrzej Wilk、Piotr Guga、Malgorzata Boczkowska

  DOI：10.1021/ja00154a001

  日期：1995.12

  Diastereomerically pure 5'-O-DMT-nucleoside 3'-O-(2-thio-1,3,2-oxathiaphospholanes) (3) and their oxathiaphospholane ring-substituted analogues (20) were used for the synthesis of stereoregular oligo(nucleoside phosphorothioate)s (S-Oligos). The oxathiaphospholane ring-opening condensation requires the presence of strong organic base, preferably DBU. The yield of a single coupling step is ca. 95% and resulting S-Oligos are free of nucleobase- and sugar-phosphorothioate backbone modifications. The diastereomeric purity of products was estimated on the basis of diastereoselective degradation with Nuclease P1 and a mixture of snake venom phosphodiesterase and Serratia marcescens endonuclease. Thermal dissociation studies of heteroduplexes S-Oligos/DNA and S-Oligos/RNA showed that their stability is stereochemistry- and sequence-dependent.
• The synthesis, X-ray and solid state NMR studies of 2-N,N-diisopropylamino-1,3,2λ5- oxaselenaphospholane-2-selone
  作者：Marek J. Potrzebowski、Jarosław BŁaszczyk、Michał W. Wieczorek、Konrad Misiura、Wojciech J. Stec

  DOI：10.1039/a606593g

  日期：——

  31 P and 77Se high resolution solid state NMR spectroscopy was employed to study structural properties of 2-N,N-diisopropylamino-1,3,2λ5- oxaselenaphospholane-2-selone 5 the compound made in the course of developing reagents for stereocontrolled synthesis of nucleoside–phosphorothioates. Both 31P CP/MAS and 77Se CP/MAS experiments revealed that the asymmetric unit consists of two independent molecules with different geometry around phosphorus and selenium centres. The principal elements δii of the 31P chemical shift tensor were calculated from spinning sideband intensities employing the WIN-MAS program. The established values of anisotropy and asymmetry parameters reflect the distortion of the phosphorus environment and correspond well with X-ray diffraction data. Crystals of 2-N,N-diisopropylamino-1,3,2λ5- oxaselenaphospholane-2-selone grown from diethyl ether are triclinic, space group P with a = 7.586(2), b = 13.003(1), c = 13.649(1) Å, α = 89.683(8)°, β = 75.42(1)°, γ = 8.74(1)°, V = 1285(6) Å3, Dc = 1.722(2) g cm-3 and Z = 4. Refinement using 5243 reflections for 235 variables gives R = 0.047.

  31P和77Se高分辨率固态核磁共振（NMR）光谱被用于研究2-N,N-二异丙基氨基-1,3,2Β5-氧杂硒杂磷杂环戊烷-2-硒酮的结构特性，该化合物是在开发用于核苷硫代磷酸酯立体控制合成的试剂的过程中合成的。31P CP/MAS和77Se CP/MAS实验均表明，不对称单元由两个围绕磷和硒中心具有不同几何形状的独立分子组成。31P化学位移张量的主要元素δii是通过使用WIN-MAS程序计算自旋边带强度得出的。已确定各向异性和不对称参数的值反映了磷环境的扭曲，并与X射线衍射数据非常吻合。从乙醚中生长出来的2-N,N-二异丙基氨基-1,3,2Β5-氧杂硒杂磷杂环戊烷-2-硒酮晶体是三斜晶系，空间群P，a=7.586(2)，b=13.003(1)，c=13.649(1)Å，α=89.683(8)°，β=75.42(1)°，γ=8.74(1)°，V=1285(6)Å