(2S)-2-[[1,3-bis(naphthalen-1-ylmethyl)-2-oxo-1,3,2lambda5-diazaphospholidin-2-yl]amino]-2-phenylacetonitrile | 1236163-01-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (2S)-2-[[1,3-bis(naphthalen-1-ylmethyl)-2-oxo-1,3,2lambda5-diazaphospholidin-2-yl]amino]-2-phenylacetonitrile
• 英文别名: (2S)-2-[[1,3-bis(naphthalen-1-ylmethyl)-2-oxo-1,3,2λ5-diazaphospholidin-2-yl]amino]-2-phenylacetonitrile
• CAS: 1236163-01-1
• 化学式: C₃₂H₂₉N₄OP
• 分子量: 516.582
• InChiKey: ZYEFPOBTOBMGQG-JGCGQSQUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  38
• 可旋转键数：
  7
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.16
• 拓扑面积：
  59.4
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2S)-2-[[1,3-bis(naphthalen-1-ylmethyl)-2-oxo-1,3,2lambda5-diazaphospholidin-2-yl]amino]-2-phenylacetonitrile 在 盐酸 、 水 作用下， 以 甲醇 为溶剂， 反应 2.0h， 生成 (S)-氨基(苯基)乙腈
  参考文献：
  名称：

  Asymmetric Catalytic N-Phosphonyl Imine Chemistry: The Use of Primary Free Amino Acids and Et₂AlCN for Asymmetric Catalytic Strecker Reaction

  摘要：

  The new asymmetric catalytic Strecker reaction of achiral N-phosphonyl imines has been established. Excellent enantioselectivity (95.2-99.7% ee) and yields (89-97%) have been achieved by using primary free natural amino acids as catalysts and Et2AlCN as nucleophile. This work also presents the novel use of nonvolatile and inexpensive Et2AlCN in asymmetric catalysis. The N-phosphonyl protecting group enabled simple product purification to be achieved simply by washing the crude products with hexane, which is defined as the GAP chemistry (GAP: Group-Assistant-Purification).(15) It can also be readily cleaved and recycled under mild condition to give a quantitative recovery of N,N'-bis(naphthalen-1-ylmethyl)ethane-1,2-diamine. A new mechanism was proposed for this reaction and was supported by experimental observations.

  DOI：

  10.1021/jo100865q
• 作为产物：
  描述：

  氰化二乙基铝 、 N-[1,3-bis(naphthalen-1-ylmethyl)-2-oxo-1,3,2lambda5-diazaphospholidin-2-yl]-1-phenylmethanimine 在 异丙醇 、 （R）-3,3''-双（[[1,1''-联苯]-4-基）-[1,1''-联萘]-2,2''-二醇 作用下， 以 甲苯 为溶剂， 反应 5.75h， 以97%的产率得到(2S)-2-[[1,3-bis(naphthalen-1-ylmethyl)-2-oxo-1,3,2lambda5-diazaphospholidin-2-yl]amino]-2-phenylacetonitrile
  参考文献：
  名称：

  Asymmetric catalytic Strecker reaction of N-phosphonyl imines with Et2AlCN using amino alcohols and BINOLs as catalysts

  摘要：

  建立了非手性 N-膦酰亚胺与 Et2AlCN 的不对称催化 Strecker 反应。游离氨基醇和联醇已被证明是有效的催化剂，可提供优异的对映选择性和产率。 N-膦酰基可以在温和条件下容易地裂解，并且可以通过用己烷简单洗涤来纯化粗产物。裂解的 N,N-二烷基二胺辅助剂可以通过正丁醇萃取定量回收。对于这种新的催化体系，对 N-膦酰亚胺和催化剂的范围进行了广泛的研究。

  DOI：

  10.1039/c0cc00287a

文献信息

• STRECKER REAGENTS, THEIR DERIVATIVES, METHODS FOR FORMING THE SAME AND IMPROVED STRECKER REACTION
  申请人：Li Guigen

  公开号：US20130137889A1

  公开（公告）日：2013-05-30

  Strecker reagents, their derivatives and methods for forming the same and improved Strecker reaction are provided. The electrophiles for asymmetric Strecker reaction include achiral N-phosphorazides, N-phosphoramides, N-phosphonyl imines and their derivatives. The nucleophiles for asymmetric Strecker reaction include chiral BINOL-derived azides, amides, imines and their derivatives, the chiral and achiral diol-based cyanides and their derivatives, the chiral and achiral diamine-based cyanides and their derivatives, the chiral and achiral amino alcohol-based cyanides and their derivatives, the Strecker nucleophiles that are derived from chiral and achiral hydroxyl carboxylic acids and amino acids. Methods of forming the electrophile for asymmetric Strecker reaction comprise the reactions with steps of: a) synthesizing phosphoryl chloride from achiral diamine; b) synthesizing phosphorous azide; c) synthesizing phosphoramide; d) synthesizing the corresponding achiral N-phosphonyl imines. The asymmetric catalytic Strecker reaction of new achiral N-phosphonyl imines has been developed to give excellent enantioselectivity (up to >99% ee) and yields (up to >97%).

  提供了Strecker试剂及其衍生物以及形成它们和改进的Strecker反应的方法。用于不对称Strecker反应的亲电试剂包括非手性N-磷酰胺、N-磷酰胺、N-磷酰亚胺及其衍生物。用于不对称Strecker反应的亲核试剂包括手性BINOL衍生的叠氮化物、酰胺、亚胺及其衍生物，手性和非手性二醇基氰化物及其衍生物，手性和非手性二胺基氰化物及其衍生物，手性和非手性氨基醇基氰化物及其衍生物，来源于手性和非手性羟基羧酸和氨基酸的Strecker亲核试剂。形成不对称Strecker反应的亲电试剂的方法包括以下步骤的反应：a)从非手性二胺合成磷酰氯；b)合成磷氮化物；c)合成磷酰胺；d)合成相应的非手性N-磷酰亚胺。新的非手性N-磷酰亚胺的不对称催化Strecker反应已经发展出具有优异的对映选择性（高达>99% ee）和产率（高达>97%）。