8-chloro-1,5-diphenylbenzo[4,5]heptaleno[1,2-e][1,3,2]dioxaphosphepin 3-oxide | 263025-90-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: 8-chloro-1,5-diphenylbenzo[4,5]heptaleno[1,2-e][1,3,2]dioxaphosphepin 3-oxide
• 英文别名: 12-chloro-17,21-diphenyl-11,13-dioxa-12λ5-phosphatetracyclo[14.5.0.02,7.09,15]henicosa-1(21),2,4,6,8,15,17,19-octaene 12-oxide
• CAS: 263025-90-7
• 化学式: C₃₀H₂₂ClO₃P
• 分子量: 496.93
• InChiKey: FQWHGFADURYLAW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  35
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  8-chloro-1,5-diphenylbenzo[4,5]heptaleno[1,2-e][1,3,2]dioxaphosphepin 3-oxide 在 sodium carbonate 作用下， 反应 1.0h， 以18%的产率得到8-hydroxy-1,5-diphenylbenzo[4,5]heptaleno[1,2-e][1,3,2]dioxaphosphepin 3-oxide
  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 、 三氯氧磷 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 4.0h， 生成 8-chloro-1,5-diphenylbenzo[4,5]heptaleno[1,2-e][1,3,2]dioxaphosphepin 3-oxide
  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