8,12-diphenylbenzo[a]heptalene-6,7-dimethyl bis(methanesulfonate) | 263172-12-9

• 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: 8,12-diphenylbenzo[a]heptalene-6,7-dimethyl bis(methanesulfonate)
• CAS: 263172-12-9
• 化学式: C₃₂H₂₈O₆S₂
• 分子量: 572.703
• InChiKey: QDPJEKVJDDEJHW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  40.0
• 可旋转键数：
  8.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  86.74
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  8,12-diphenylbenzo[a]heptalene-6,7-dimethyl bis(methanesulfonate) 在 三乙烯二胺 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 4.0h， 生成 (-)-(P)-6,7-bis[(diphenylphosphanyl)methyl]-8,12-diphenylbenzo[a]heptalene
  参考文献：
  名称：

  Synthesis of (P)- and (M)-6,7-Bis[(diphenylphosphanyl)methyl]-8,12-diphenylbenzo[a]heptalenes - Potential Ligands for Homogeneous Asymmetric Catalysis

  摘要：

  The title bis(phosphane) ligands have been prepared starting from optically pure diisopropyl (P)- and (M)-8,22-diphenylbenzo[a]heptalene-6,7-dicarboxylaes ((P)-1b and (M)-1b) that had been obtained by HPLC separation of rac-1b on a semi-preparative Chiralcel OD column. Reduction of (P)-1b and (M)-1b with diisobutylaluminum hydride (DIBAH) gave optically pure (P)- and (M)-dimethanols 3 (Scheme 6 and Fig. 5). Unfortunately, the almost quantitative chlorination of rac-3 with PCl5 in CHCl3 at - 60 degrees led with (M)-3 to nearly complete loss of optical integrity However, mesylate formation of (P)-3. followed by phosphanylation with LiP(BH3)Ph-2 gave (P)-6 with only a small loss of optical activity. Optically pure (P)-6 was obtained by crystallization from Et2O/hexane, which removed the nearly insoluble rac-6. The pure bis(phosphane) ligands (P)-2 and (M)-2 can be liberated quantitatively from 6 by warming 6 in toluene in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO). First Rh'-catalyzed asymmetric hydrogenation reactions of (Z)-alpha-(acetamido)cinnamic acid ((Z)-14) in the presence of (P)-2 led to (R)-N-acetylphenylalanin ((R)-15) in optical purities up to 77% (see Table 1).

  DOI：

  10.1002/(sici)1522-2675(20000119)83:1<258::aid-hlca258>3.0.co;2-a
• 作为产物：
  描述：

  diisopropyl 8,12-diphenylbenzo[a]heptalene-6,7-dicarboxylate 在 二异丁基氢化铝 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 5.5h， 生成 8,12-diphenylbenzo[a]heptalene-6,7-dimethyl bis(methanesulfonate)
  参考文献：
  名称：

  Synthesis of (P)- and (M)-6,7-Bis[(diphenylphosphanyl)methyl]-8,12-diphenylbenzo[a]heptalenes - Potential Ligands for Homogeneous Asymmetric Catalysis

  摘要：

  The title bis(phosphane) ligands have been prepared starting from optically pure diisopropyl (P)- and (M)-8,22-diphenylbenzo[a]heptalene-6,7-dicarboxylaes ((P)-1b and (M)-1b) that had been obtained by HPLC separation of rac-1b on a semi-preparative Chiralcel OD column. Reduction of (P)-1b and (M)-1b with diisobutylaluminum hydride (DIBAH) gave optically pure (P)- and (M)-dimethanols 3 (Scheme 6 and Fig. 5). Unfortunately, the almost quantitative chlorination of rac-3 with PCl5 in CHCl3 at - 60 degrees led with (M)-3 to nearly complete loss of optical integrity However, mesylate formation of (P)-3. followed by phosphanylation with LiP(BH3)Ph-2 gave (P)-6 with only a small loss of optical activity. Optically pure (P)-6 was obtained by crystallization from Et2O/hexane, which removed the nearly insoluble rac-6. The pure bis(phosphane) ligands (P)-2 and (M)-2 can be liberated quantitatively from 6 by warming 6 in toluene in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO). First Rh'-catalyzed asymmetric hydrogenation reactions of (Z)-alpha-(acetamido)cinnamic acid ((Z)-14) in the presence of (P)-2 led to (R)-N-acetylphenylalanin ((R)-15) in optical purities up to 77% (see Table 1).

  DOI：

  10.1002/(sici)1522-2675(20000119)83:1<258::aid-hlca258>3.0.co;2-a