(R,S)-(3'lu)-1,3-dibenzyldihydro-2-(3'-methyl-2'-oxo-5'-hexen-1'-yl)-3H-1,3,2-dibenzodiazaphosphepine 2-oxide | 135614-39-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氮杂萘
• 英文名称: (R,S)-(3'lu)-1,3-dibenzyldihydro-2-(3'-methyl-2'-oxo-5'-hexen-1'-yl)-3H-1,3,2-dibenzodiazaphosphepine 2-oxide
• 英文别名: (R,S)-(3'lu)-1,3-dibenzyldihydro-2-(3'-methyl-2'-oxo-5'-hexen-1'-yl)-3H-1,3,2-dibenzo[d,f]diazaphosphepine 2-oxide；1-(5,7-Dibenzyl-1,11-dimethyl-6-oxobenzo[d][1,3,2]benzodiazaphosphepin-6-yl)-3-methylhex-5-en-2-one
• CAS: 135614-39-0；135614-45-8
• 化学式: C₃₅H₃₇N₂O₂P
• 分子量: 548.665
• InChiKey: UJOXDFCEDAUTRW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.2
• 重原子数：
  40
• 可旋转键数：
  9
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  40.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  N,N'-dibenzylidene-6,6'-dimethyl-2,2'-biphenyldiamine 在 N-甲基吗啉 、 sodium tetrahydroborate 、 sodium hydride 、 三乙胺 、 叔丁醇 、 三氯化磷 作用下， 以 甲醇 、 甲苯 为溶剂， 反应 4.5h， 生成 (R,S)-(3'lu)-1,3-dibenzyldihydro-2-(3'-methyl-2'-oxo-5'-hexen-1'-yl)-3H-1,3,2-dibenzodiazaphosphepine 2-oxide
  参考文献：
  名称：

  Carbanion-accelerated Claisen rearrangements. 8. Phosphonamide anion-stabilizing groups

  摘要：

  The utility of various phosphonamide groups has been examined in the context of the carbanion-accelerated Claisen rearrangement (CACR). An extensive survey has identified the N,N'-dibenzyl-1,3,2-diazaphospholidine group 11 to be optimal in the ease of construction of the CACR precursors and the facility and stereoselectivity of the rearrangement. Using n-butyllithium as the base, the phosphonamides rearranged readily at -20-degrees-C with complete regioselectivity and in good yield (74-79%). The phosphonates also showed a high level of diastereoselectivity (> 95% de) but the yield from the (Z)-2-butenyl precursor (anti product) was only 45%. A chiral N,N'-dibenzyl-1,3,2-diazaphospholidine 12 derived from trans-1,2-cyclohexanediamine was examined. Although the CACR proceeded very cleanly (71-85%) and with high internal selectivity (94% de), the relative asymmetric induction was poor (16-20% de). This was also the case for a chiral N,N'-dibenzyl-1,3,2-diazaphosphorinane 15 derived from (R,R)-1,3-diphenyl-1,3-propanediamine and N,N'-dibenzyl-1,3,2-diazaphosphepine 16 derived from 6,6'-dimethyl-2,2'-diaminobiphenyl. The characteristic features of the CACR were compared with the aryl sulfone and phosphonate versions.

  DOI：

  10.1021/jo00017a016