4-(di-tert-butylphosphino)-N,N-dimethylpiperidinium chloride | 360577-24-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: 4-(di-tert-butylphosphino)-N,N-dimethylpiperidinium chloride
• 英文别名: 4-(di-t-butylphosphino)-N,N-dimethylpiperidinium chloride；ditert-butyl-(1,1-dimethylpiperidin-1-ium-4-yl)phosphane;chloride
• CAS: 360577-24-8
• 化学式: C₁₅H₃₃NP*Cl
• 分子量: 293.86
• InChiKey: PISRMQALIIQVDX-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.31
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-(di-tert-butylphosphino)-N,N-dimethylpiperidinium chloride 、 palladium diacetate 在 phenylboronic acid 、 Na₂CO₃ 作用下， 以 水 、 乙腈 为溶剂， 生成 [(4-(di-tert-butylphosphino)-N,N-dimethylpiperidinium)2Pd]Cl2
  参考文献：
  名称：

  Experimental and Computational Study of Steric and Electronic Effects on the Coordination of Bulky, Water-Soluble Alkylphosphines to Palladium under Reducing Conditions:  Correlation to Catalytic Activity

  摘要：

  Sterically demanding, water-soluble alkylphosphine ligands 2-(di-tert-butylphosphino)ethyltrimethylammonium chloride (t-Bu-Amphos) and 4-(di-tert-butylphosphino)-N,N-di-methylpiperidinium chloride (t-Bu-Pip-phos) in combination with palladium salts provided active catalysts for the cross-coupling of aryl halides under mild conditions in aqueous solvents, whereas 4-(dicyclohexylphosphino)-N,N-dimethylpiperidinium chloride (Cy-Pip-phos) gave a less active catalyst. Catalyst activity increased with increasing cone angle of the ligands, but the chi electronic parameter determined from the symmetric C-O stretching frequency of LNi(CO)(3) did not correlate with catalyst activity. Catalyst activity correlated with other calculated electronic parameters, such as the HOMO-LUMO energy gap of the ligand and the HOMO energy level of the LPd(0) species. Multinuclear NMR spectroscopic studies showed that t-Bu-Amphos and t-Bu-Pip-phos rapidly form L2Pd(0) (L = t-Bu-Amphos or t-Bu-Pip-phos) complexes when reacted with Pd(OAc)(2) under reducing conditions over a range of L:Pd ratios. In contrast, the coordination chemistry of Cy-Pip-phos depended on the Cy-Pip-phos:Pd ratio. At a less than or equal to 1: 1 Cy-Pip-phos:Pd ratio, rapid formation of L2Pd(0) occurred. At higher L:Pd ratios, initial formation of trans-(Cy-Pip-phos)(2)PdCl2 was observed followed by slow reduction to the Pd(0) complex.

  DOI：

  10.1021/om049241w
• 作为产物：
  描述：

  在 吗啉 作用下， 反应 4.0h， 以58%的产率得到4-(di-tert-butylphosphino)-N,N-dimethylpiperidinium chloride
  参考文献：
  名称：

  Sterically Demanding, Water-Soluble Alkylphosphines as Ligands for High Activity Suzuki Coupling of Aryl Bromides in Aqueous Solvents

  摘要：

  [GRAPHICS]Sterically demanding, water-soluble alkylphosphines have been found to give highly active catalysts for Suzuki coupling of aryl bromides in aqueous solvents. A variety of aryl bromides and boronic acids were coupled in excellent yield. Turnover numbers up to 734 000 mmol/mmol Pd have been achieved under mild conditions.

  DOI：

  10.1021/ol0163629
• 作为试剂：
  描述：

  N-(叔丁氧羰基)-对溴-DL-苯丙氨酸 、 4-甲氧基苯硼酸 在 palladium diacetate 4-(di-tert-butylphosphino)-N,N-dimethylpiperidinium chloride 、 sodium carbonate 作用下， 以 水 、 乙腈 为溶剂， 反应 2.0h， 以94%的产率得到rac-2-{[(tert-butyloxy)carbonyl]amino}-3-(4'-methoxybiphenyl-4-yl)propionic acid
  参考文献：
  名称：

  使用水溶性，立体要求高的烷基膦在温和条件下水相，钯催化的芳族溴化物的交叉偶联

  摘要：

  要求严格的水溶性烷基膦化合物已与Suzuki，Sonogashira的各种钯盐和芳基溴化物的Heck偶联剂在温和条件下于水性溶剂中结合使用。的叔丁基取代的配体的2-（二-叔-butylphosphino）乙基三甲基氯化铵（吨-Bu-Amphos）和4-（二-叔-butylphosphino） - N，N-二甲基哌啶氯化物（吨发现-Bu-Pip-phos与钯（II）盐的结合所产生的催化剂的活性明显高于衍生自三（3-磺酰基苯基）膦三钠（TPPTS）的催化剂。未活化的芳基溴化物的Suzuki偶联在室温下在水/乙腈和水/甲苯两相混合物中或在纯水中有效地发生。值得注意的是，亲水性芳基溴化物的Suzuki偶联反应不使用有机溶剂进行反应或提纯即可获得高收率。该方法已被应用于高效二氟尼醛的合成。来自t的催化剂-Bu-Amphos在水/甲苯中的Suzuki偶联剂中循环了3次，然后催化剂活性开始显着下降。四个循环的平均产率为每个循环>

  DOI：

  10.1021/jo048910c

文献信息

• HOMOGENEOUS ERYTHROPOIETIN AND METHOD FOR THEIR PREPARATION
  申请人：Sloan-Kettering Institute for Cancer Research

  公开号：EP2010556B1

  公开（公告）日：2015-09-23
• Homogeneous Erythropoietin and Other Peptides and Proteins, Methods and Intermediates for Their Preparation
  申请人：Danishefsky Samuel J.

  公开号：US20100081786A1

  公开（公告）日：2010-04-01

  The present invention provides isolated homogeneous polyfunctionalized proteins (e.g., erythropoietin), isolated glycopeptides, and a method for preparing polyfunctionalized peptides and/or proteins via cysteine-free native chemical ligation. In certain embodiments, the invention provides an isolated homogeneous polyfunctionalized protein having the structure (I). In certain other embodiments, the invention provides an isolated glycopeptide having Formula (II). In certain other embodiments, the inventive method is a method for preparing a polyfunctionalized peptide comprising a peptidic backbone made up of four or more amino acids, wherein two or more non-adjacent amino acids are independently substituted with a moiety having the structure (III)-LH. wherein A and L1 are as defined herein.
• US8754192B2
  申请人：——

  公开号：US8754192B2

  公开（公告）日：2014-06-17
• Sterically Demanding, Water-Soluble Alkylphosphines as Ligands for High Activity Suzuki Coupling of Aryl Bromides in Aqueous Solvents
  作者：Kevin H. Shaughnessy、Rebecca S. Booth

  DOI：10.1021/ol0163629

  日期：2001.8.1

  [GRAPHICS]Sterically demanding, water-soluble alkylphosphines have been found to give highly active catalysts for Suzuki coupling of aryl bromides in aqueous solvents. A variety of aryl bromides and boronic acids were coupled in excellent yield. Turnover numbers up to 734 000 mmol/mmol Pd have been achieved under mild conditions.
• Experimental and Computational Study of Steric and Electronic Effects on the Coordination of Bulky, Water-Soluble Alkylphosphines to Palladium under Reducing Conditions:  Correlation to Catalytic Activity
  作者：Rebecca B. DeVasher、Jason M. Spruell、David A. Dixon、Grant A. Broker、Scott T. Griffin、Robin D. Rogers、Kevin H. Shaughnessy

  DOI：10.1021/om049241w

  日期：2005.2.1

  Sterically demanding, water-soluble alkylphosphine ligands 2-(di-tert-butylphosphino)ethyltrimethylammonium chloride (t-Bu-Amphos) and 4-(di-tert-butylphosphino)-N,N-di-methylpiperidinium chloride (t-Bu-Pip-phos) in combination with palladium salts provided active catalysts for the cross-coupling of aryl halides under mild conditions in aqueous solvents, whereas 4-(dicyclohexylphosphino)-N,N-dimethylpiperidinium chloride (Cy-Pip-phos) gave a less active catalyst. Catalyst activity increased with increasing cone angle of the ligands, but the chi electronic parameter determined from the symmetric C-O stretching frequency of LNi(CO)(3) did not correlate with catalyst activity. Catalyst activity correlated with other calculated electronic parameters, such as the HOMO-LUMO energy gap of the ligand and the HOMO energy level of the LPd(0) species. Multinuclear NMR spectroscopic studies showed that t-Bu-Amphos and t-Bu-Pip-phos rapidly form L2Pd(0) (L = t-Bu-Amphos or t-Bu-Pip-phos) complexes when reacted with Pd(OAc)(2) under reducing conditions over a range of L:Pd ratios. In contrast, the coordination chemistry of Cy-Pip-phos depended on the Cy-Pip-phos:Pd ratio. At a less than or equal to 1: 1 Cy-Pip-phos:Pd ratio, rapid formation of L2Pd(0) occurred. At higher L:Pd ratios, initial formation of trans-(Cy-Pip-phos)(2)PdCl2 was observed followed by slow reduction to the Pd(0) complex.