[4-(2,2-dimethyl-1,3-dioxolan-4-yl)-1-butenyl]pentamethyl phosphoric triamide

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: [4-(2,2-dimethyl-1,3-dioxolan-4-yl)-1-butenyl]pentamethyl phosphoric triamide
• 英文别名: (E)-N-[bis(dimethylamino)-oxidophosphaniumyl]-4-(2,2-dimethyl-1,3-dioxolan-4-yl)-N-methylbut-1-en-1-amine
• 化学式: C₁₄H₃₀N₃O₃P
• 分子量: 319.384
• InChiKey: ALTRKDWGSGQQEC-PKNBQFBNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  51.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  [4-(2,2-dimethyl-1,3-dioxolan-4-yl)-1-butenyl]pentamethyl phosphoric triamide 在 硫酸 作用下， 以 乙醚 、 水 为溶剂， 反应 1.5h， 以87%的产率得到4-(2,2-dimethyl-1,3-dioxolan-4-yl)butanal
  参考文献：
  名称：

  A general synthesis of 2- or 3-alkyl substituted 5-hydroxymethyl-δ-valerolactones, precursors of 5-formyl-δ-valerolactones, via lithiated N-allyl(bisdimethylamino)-N-methylphosphoramide carbanions

  摘要：

  A convenient strategy is reported for the synthesis of 2- or 3-alkylsubstituted 5-hydroxymethyl and 5-formyl-delta-valerolactones, which are very useful starting blocks for the total synthesis of leukotrienes and lactonic pheromones, It has been found that lithiated enephosphoramide ambident anions reacted exclusively in the gamma position with 2,3-O-isopropylidene glycerol triflate to give corresponding alkylated enephosphoramides by a C3-C3 backbone connection. Enephosphoramide group was further selectively hydrolyzed in the presence of isopropylidene function in mild acidic conditions and led to expected aldehydes in high yields. Oxidation of these aldehydes using silver oxide or potassium permanganate afforded corresponding acids. Further hydrolysis of the isopropylidene group led to unstable dihydroxyacids which directly lactonized. The latter were converted to 5-formyl-delta-valerolactones using PDC oxidant. (C) 1999 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(99)00269-7
• 作为产物：
  描述：

  N-allyl-N-methyl-(bisdimethylamino) phosphoramide 、 trifluoromethanesulfonic acid (2,2-dimethyl-1,3-dioxolan-4-yl)methyl ester 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以78%的产率得到[4-(2,2-dimethyl-1,3-dioxolan-4-yl)-1-butenyl]pentamethyl phosphoric triamide
  参考文献：
  名称：

  A general synthesis of 2- or 3-alkyl substituted 5-hydroxymethyl-δ-valerolactones, precursors of 5-formyl-δ-valerolactones, via lithiated N-allyl(bisdimethylamino)-N-methylphosphoramide carbanions

  摘要：

  A convenient strategy is reported for the synthesis of 2- or 3-alkylsubstituted 5-hydroxymethyl and 5-formyl-delta-valerolactones, which are very useful starting blocks for the total synthesis of leukotrienes and lactonic pheromones, It has been found that lithiated enephosphoramide ambident anions reacted exclusively in the gamma position with 2,3-O-isopropylidene glycerol triflate to give corresponding alkylated enephosphoramides by a C3-C3 backbone connection. Enephosphoramide group was further selectively hydrolyzed in the presence of isopropylidene function in mild acidic conditions and led to expected aldehydes in high yields. Oxidation of these aldehydes using silver oxide or potassium permanganate afforded corresponding acids. Further hydrolysis of the isopropylidene group led to unstable dihydroxyacids which directly lactonized. The latter were converted to 5-formyl-delta-valerolactones using PDC oxidant. (C) 1999 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(99)00269-7

文献信息

• 5-formyl-δ—valerolactone : A useful synthon for the chiral synthesis of the vespa orientalis pheromone and the mosquito oviposition attractant pheromone
  作者：Ph. Coutrot、C. Grison、C. Bômont

  DOI：10.1016/s0040-4039(00)74412-1

  日期：1994.11

  A synthetic scheme starting from the reaction between the lithiated N-allyl-N-methyl-(bisdimethylamino)phosphoramide anion and the triflate derivative of (R)-(-)- or (S)-(+)-2,3-O-isopropylideneglycerol is described to prepare the key chiral synthon (R)-5- or (S)-5-formyl-delta-valerolactone that leads to the title compounds.
• A general synthesis of 2- or 3-alkyl substituted 5-hydroxymethyl-δ-valerolactones, precursors of 5-formyl-δ-valerolactones, via lithiated N-allyl(bisdimethylamino)-N-methylphosphoramide carbanions
  作者：Philippe Coutrot、Claude Grison、Catherine Bômont

  DOI：10.1016/s0022-328x(99)00269-7

  日期：1999.9

  A convenient strategy is reported for the synthesis of 2- or 3-alkylsubstituted 5-hydroxymethyl and 5-formyl-delta-valerolactones, which are very useful starting blocks for the total synthesis of leukotrienes and lactonic pheromones, It has been found that lithiated enephosphoramide ambident anions reacted exclusively in the gamma position with 2,3-O-isopropylidene glycerol triflate to give corresponding alkylated enephosphoramides by a C3-C3 backbone connection. Enephosphoramide group was further selectively hydrolyzed in the presence of isopropylidene function in mild acidic conditions and led to expected aldehydes in high yields. Oxidation of these aldehydes using silver oxide or potassium permanganate afforded corresponding acids. Further hydrolysis of the isopropylidene group led to unstable dihydroxyacids which directly lactonized. The latter were converted to 5-formyl-delta-valerolactones using PDC oxidant. (C) 1999 Elsevier Science S.A. All rights reserved.