1,3-dibenzyl-2-(3',3'-dimethyl-2'-oxo-5'-hexen-1'-yl)-1,3,2-diazaphosphorinane 2-oxide | 135614-37-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,3-dibenzyl-2-(3',3'-dimethyl-2'-oxo-5'-hexen-1'-yl)-1,3,2-diazaphosphorinane 2-oxide
• 英文别名: 1-(1,3-Dibenzyl-2-oxo-1,3,2lambda5-diazaphosphinan-2-yl)-3,3-dimethylhex-5-en-2-one；1-(1,3-dibenzyl-2-oxo-1,3,2λ5-diazaphosphinan-2-yl)-3,3-dimethylhex-5-en-2-one
• CAS: 135614-37-8
• 化学式: C₂₅H₃₃N₂O₂P
• 分子量: 424.523
• InChiKey: NSTGRSQUTXUDER-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  30
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 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’-二苯基-1,3-丙二胺 在 N-甲基吗啉 、 正丁基锂 、 sodium hydride 、 三乙胺 、 叔丁醇 、 三氯化磷 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 15.75h， 生成 1,3-dibenzyl-2-(3',3'-dimethyl-2'-oxo-5'-hexen-1'-yl)-1,3,2-diazaphosphorinane 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

文献信息

• Carbanion-accelerated Claisen rearrangements. 8. Phosphonamide anion-stabilizing groups
  作者：Scott E. Denmark、Heinz Stadler、Roberta L. Dorow、Jung Ho Kim

  DOI：10.1021/jo00017a016

  日期：1991.8

  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.