[(3,7-Diacetyl-1,3,7-triaza-5lambda5-phosphabicyclo[3.3.1]nonan-5-ylidene)amino]-diphenoxy-sulfidophosphanium | 1418001-32-7

• 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: [(3,7-Diacetyl-1,3,7-triaza-5lambda5-phosphabicyclo[3.3.1]nonan-5-ylidene)amino]-diphenoxy-sulfidophosphanium
• 英文别名: [(3,7-diacetyl-1,3,7-triaza-5λ5-phosphabicyclo[3.3.1]nonan-5-ylidene)amino]-diphenoxy-sulfidophosphanium
• CAS: 1418001-32-7
• 化学式: C₂₁H₂₆N₄O₄P₂S
• 分子量: 492.475
• InChiKey: BBZYTJBFYYIACW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  32
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  75.7
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  silver hexafluoroantimonate 、 [(3,7-Diacetyl-1,3,7-triaza-5lambda5-phosphabicyclo[3.3.1]nonan-5-ylidene)amino]-diphenoxy-sulfidophosphanium 以 二氯甲烷 为溶剂， 反应 1.0h， 以91%的产率得到[Ag{μ²-O,S-(3,7-diacetyl-1,3,5-triaza-5-phospha-bicyclo[3.3.1]nonane)=NP(=S)(OPh)₂}]_x[SbF₆]_x
  参考文献：
  名称：

  New Ag(I)–Iminophosphorane Coordination Polymers as Efficient Catalysts Precursors for the MW-Assisted Meyer–Schuster Rearrangement of Propargylic Alcohols in Water

  摘要：

  Treatment of the N-thiophosphorylated iminophosphorane ligands (PTA)=NP(=S)(OR)(2) [PTA = 1,3,5-triaza-7-phosphaadamantane, 3a and 3b] and (DAPTA)=NP(=S)(OR)(2) [DAPTA = 3,7-diacetyl-1,3,7-triaza-5-bicyclo[3.3.1]nonane, 4a and 4b] with an equimolecular amount of AgSbF6 leads to high-yield formation of the new one-dimensional coordination polymers [Ag{mu(2)-N,S-(PTA)=NP(=S)(OR)(2)}](x)[SbF6](x) (5a and 5b) and [Ag{mu(2)-O,S(DAPTA)=NP(=S)(OR)(2)}](x)[SbF6](x) (6a and 6b), respectively. These new (iminophosphorane)silver(I) coordination polymers are efficient catalyst precursors for the Meyer-Schuster isomerization of both terminal and internal alkynols. Reactions proceeded in water, under aerobic conditions and using microwave irradiation as heating source, to afford the corresponding alpha,beta-unsaturated carbonyl compounds in excellent yields, without the addition of any cocatalyst. Remarkably, it should be noted that this catalytic system can be recycled up to 10 consecutive runs (1st cycle 45 min, 99%; 10th cycle 6 h, 97%). ESI-MS analysis of 5a in water has been carried out providing valuable insight into the monomeric active species responsible for catalytic activity in water.

  DOI：

  10.1021/ic400511d
• 作为产物：
  描述：

  azidodiphenoxyphosphine oxide 、 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane 以 四氢呋喃 为溶剂， 反应 6.0h， 以83%的产率得到[(3,7-Diacetyl-1,3,7-triaza-5lambda5-phosphabicyclo[3.3.1]nonan-5-ylidene)amino]-diphenoxy-sulfidophosphanium
  参考文献：
  名称：

  （亚氨基正膦）铜（I）配合物作为高效催化剂，用于在水中对具有末端和 1-碘炔烃的叠氮化物进行 1,3-偶极环加成反应：炔烃和原位生成叠氮化物的一锅多组分反应

  摘要：

  用等分子量的叠氮化物 (RO)2P(=S)N3 (R = Et, Ph) 处理水溶性磷烷 PTA (1) 和 DAPTA (2) 导致 N-硫代磷酸化亚氨基正膦衍生物的高产率形成分别为 3b 和 4a,b。已经研究了这些新的亚氨基正膦配体与 [Cu(NCCH3)4][PF6]（摩尔比为 2:1）的反应。所得（亚氨基正膦）铜（I）配合物 5b 和 6a,b 是三组分环加成反应（有机卤化物、NaN3 和末端炔烃）在水性介质中的有效催化剂，根据“点击法律”，具有广泛底物范围和功能兼容性的 1,4-二取代三唑。还报道了类似的（亚氨基正膦）铜（I）催化剂 5a 在水介质中以 1-碘炔作为内部炔的一锅三组分反应中的前所未有的应用。已经进行了水中 5a 的 ESI-MS 分析和 DFT 理论计算 [B3LYP/6-31G(d)]，为了解负责水中催化活性的实际活性物质提供了宝贵的见解。

  DOI：

  10.1002/ejic.201200789

文献信息

• New Ag(I)–Iminophosphorane Coordination Polymers as Efficient Catalysts Precursors for the MW-Assisted Meyer–Schuster Rearrangement of Propargylic Alcohols in Water
  作者：Joaquín García-Álvarez、Josefina Díez、Cristian Vidal、Cristian Vicent

  DOI：10.1021/ic400511d

  日期：2013.6.3

  Treatment of the N-thiophosphorylated iminophosphorane ligands (PTA)=NP(=S)(OR)(2) [PTA = 1,3,5-triaza-7-phosphaadamantane, 3a and 3b] and (DAPTA)=NP(=S)(OR)(2) [DAPTA = 3,7-diacetyl-1,3,7-triaza-5-bicyclo[3.3.1]nonane, 4a and 4b] with an equimolecular amount of AgSbF6 leads to high-yield formation of the new one-dimensional coordination polymers [Agmu(2)-N,S-(PTA)=NP(=S)(OR)(2)}](x)[SbF6](x) (5a and 5b) and [Agmu(2)-O,S(DAPTA)=NP(=S)(OR)(2)}](x)[SbF6](x) (6a and 6b), respectively. These new (iminophosphorane)silver(I) coordination polymers are efficient catalyst precursors for the Meyer-Schuster isomerization of both terminal and internal alkynols. Reactions proceeded in water, under aerobic conditions and using microwave irradiation as heating source, to afford the corresponding alpha,beta-unsaturated carbonyl compounds in excellent yields, without the addition of any cocatalyst. Remarkably, it should be noted that this catalytic system can be recycled up to 10 consecutive runs (1st cycle 45 min, 99%; 10th cycle 6 h, 97%). ESI-MS analysis of 5a in water has been carried out providing valuable insight into the monomeric active species responsible for catalytic activity in water.
• (Iminophosphorane)copper(I) Complexes as Highly Efficient Catalysts for 1,3‐Dipolar Cycloaddition of Azides with Terminal and 1‐Iodoalkynes in Water: One‐Pot Multi‐Component Reaction from Alkynes and in situ Generated Azides
  作者：Joaquín García‐Álvarez、Josefina Díez、Jose Gimeno、Francisco J. Suárez、Cristian Vincent

  DOI：10.1002/ejic.201200789

  日期：2012.12

  amount of azides (RO)2P(=S)N3 (R = Et, Ph) leads to high-yield formation of the N-thiophosphorylated iminophosphorane derivatives 3b and 4a,b, respectively. The reaction of these new iminophosphorane ligands with [Cu(NCCH3)4][PF6] (in a 2:1 molar ratio) has been investigated. The resulting (iminophosphorane)copper(I) complexes 5b and 6a,b are efficient catalysts for the three-component cycloaddition reaction

  用等分子量的叠氮化物 (RO)2P(=S)N3 (R = Et, Ph) 处理水溶性磷烷 PTA (1) 和 DAPTA (2) 导致 N-硫代磷酸化亚氨基正膦衍生物的高产率形成分别为 3b 和 4a,b。已经研究了这些新的亚氨基正膦配体与 [Cu(NCCH3)4][PF6]（摩尔比为 2:1）的反应。所得（亚氨基正膦）铜（I）配合物 5b 和 6a,b 是三组分环加成反应（有机卤化物、NaN3 和末端炔烃）在水性介质中的有效催化剂，根据“点击法律”，具有广泛底物范围和功能兼容性的 1,4-二取代三唑。还报道了类似的（亚氨基正膦）铜（I）催化剂 5a 在水介质中以 1-碘炔作为内部炔的一锅三组分反应中的前所未有的应用。已经进行了水中 5a 的 ESI-MS 分析和 DFT 理论计算 [B3LYP/6-31G(d)]，为了解负责水中催化活性的实际活性物质提供了宝贵的见解。