trans-(t-Bu)(H)(i-Bu)B2(OTf)P2(i-Pr)2 | 1189341-56-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: trans-(t-Bu)(H)(i-Bu)B2(OTf)P2(i-Pr)2
• 英文别名: (t-Bu)(H)(i-Bu)B2(trifluoromethanesulfonate)P2(i-Pr)2；[4-Tert-butyl-2-(2-methylpropyl)-1,1,3,3-tetra(propan-2-yl)-1,3-diphosphonia-2,4-diboranuidacyclobut-2-yl] trifluoromethanesulfonate
• CAS: 1189341-56-7
• 化学式: C₂₁H₄₇B₂F₃O₃P₂S
• 分子量: 520.233
• InChiKey: RUCXPXQMGVWIQE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.15
• 重原子数：
  32
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  三氟甲磺酸 、 1,3-di(tert-butyl)-2,2,4,4-tetraisopropyl-1,3-dibora-2,4-diphosphoniocyclobutane-1,3-diyl 以 甲苯 为溶剂， 反应 1.0h， 以45%的产率得到trans-(t-Bu)(H)(i-Bu)B2(OTf)P2(i-Pr)2
  参考文献：
  名称：

  Ionic-Type Reactivity of 1,3-Dibora-2,4-diphosphoniocyclobutane-1,3-diyls: Regio- and Stereoselective Addition of Hydracids

  摘要：

  Hydrogen chloride and trifluoromethane sulfonic acid readily add to the symmetrically substituted 1,3-dibora-2,4-diphosphoniocyclobutane-1,3-diyl (1) and unsymmetrically substituted 1,3-dibora-2,4-diphosphoniobicyclo[1.1.0]butane (3) under mild conditions, substantiating some formal analogies between the PBPB diradicaloids D and alkenes. X-ray diffraction analyses carried out on all the resulting 1,3-diborata-2,4-diphosphoniocyclobutanes (2, 4-6) revealed that the reactions proceed with complete stereo- and regio-selectivity, and that an unusual t-Bu -> i-Bu isomerization can occur at boron. DFT calculations shed more light on the factors controlling the regioselectivity of the additions, its concerted versus stepwise character, and support an original two-step mechanism for the t-Bu -> i-Bu isomerization, involving a carbocationic sigma-borane adduct as a key intermediate.

  DOI：

  10.1021/ja903746p