Cy2P(S)CH2NHtBu | 1234313-17-7

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机硫代磷化合物
• 英文名称: Cy2P(S)CH2NHtBu
• 英文别名: (Tert-butylamino)methyl-dicyclohexyl-sulfidophosphanium；(tert-butylamino)methyl-dicyclohexyl-sulfidophosphanium
• CAS: 1234313-17-7
• 化学式: C₁₇H₃₄NPS
• 分子量: 315.503
• InChiKey: PRUIMPWYHSNMAY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  13
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  Cy2P(S)CH2NHtBu 、 碘甲烷 在 甲基锂 作用下， 以 甲苯 为溶剂， 以84%的产率得到dicyclohexylmethylphosphine sulfide
  参考文献：
  名称：

  Phosphine- and thiophosphorane-amine ligands: Lithiation and coordination to Rh(I)

  摘要：

  A series of phosphine-amine and thiophosphorane-amine ligands (PR2(X)CH2NHR', X = lone pair, S, R = Ph, Cy, R' = tBu, Ph) differing by the nature of the phosphorus and nitrogen substituents were synthesized. Their lithiation, in order to generate the corresponding amido ligand mainly led to dissociation with formation of phosphide or thiophosphinite anion and imine. DFT calculations confirmed that this pathway is in most cases thermodynamically favoured. But for a phosphine-amido anion featuring alkyl substituents on the P atom and phenyl on the nitrogen, calculations showed that the dissociation is strongly disfavoured (Delta G = +24.3 kcal mol(-1)). Actually, {PCy2CH2NPhLi} was isolated in high yield and fully characterized. This phosphine-amido ligand and the corresponding amine derivative were then coordinated to Rh(I) metal centre. (C) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2010.03.006
• 作为产物：
  描述：

  Cy2PCH2NHtBu 在 1,2,3,4,5,6,7,8-八硫杂环辛烷 作用下， 以 甲苯 为溶剂， 反应 0.5h， 以97%的产率得到Cy2P(S)CH2NHtBu
  参考文献：
  名称：

  Phosphine- and thiophosphorane-amine ligands: Lithiation and coordination to Rh(I)

  摘要：

  A series of phosphine-amine and thiophosphorane-amine ligands (PR2(X)CH2NHR', X = lone pair, S, R = Ph, Cy, R' = tBu, Ph) differing by the nature of the phosphorus and nitrogen substituents were synthesized. Their lithiation, in order to generate the corresponding amido ligand mainly led to dissociation with formation of phosphide or thiophosphinite anion and imine. DFT calculations confirmed that this pathway is in most cases thermodynamically favoured. But for a phosphine-amido anion featuring alkyl substituents on the P atom and phenyl on the nitrogen, calculations showed that the dissociation is strongly disfavoured (Delta G = +24.3 kcal mol(-1)). Actually, {PCy2CH2NPhLi} was isolated in high yield and fully characterized. This phosphine-amido ligand and the corresponding amine derivative were then coordinated to Rh(I) metal centre. (C) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2010.03.006

文献信息

• Phosphine- and thiophosphorane-amine ligands: Lithiation and coordination to Rh(I)
  作者：Elina Payet、Audrey Auffrant、Xavier F. Le Goff、Pascal Le Floch

  DOI：10.1016/j.jorganchem.2010.03.006

  日期：2010.5

  A series of phosphine-amine and thiophosphorane-amine ligands (PR2(X)CH2NHR', X = lone pair, S, R = Ph, Cy, R' = tBu, Ph) differing by the nature of the phosphorus and nitrogen substituents were synthesized. Their lithiation, in order to generate the corresponding amido ligand mainly led to dissociation with formation of phosphide or thiophosphinite anion and imine. DFT calculations confirmed that this pathway is in most cases thermodynamically favoured. But for a phosphine-amido anion featuring alkyl substituents on the P atom and phenyl on the nitrogen, calculations showed that the dissociation is strongly disfavoured (Delta G = +24.3 kcal mol(-1)). Actually, PCy2CH2NPhLi} was isolated in high yield and fully characterized. This phosphine-amido ligand and the corresponding amine derivative were then coordinated to Rh(I) metal centre. (C) 2010 Elsevier B.V. All rights reserved.