N-(1-methylbenzyl)amino-tert-butylphenylphosphine | 220812-79-3

• 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: N-(1-methylbenzyl)amino-tert-butylphenylphosphine
• 英文别名: (S)-(1-phenylethylamino)(tert-butyl)phenylphosphine；(S)-N-(1-phenylethyl)amino-tert-butylphenylphosphine；(S(p))/(R(p))-tert-butyl(α-methylbenzylamino)phenylphosphine；(1S)-N-[tert-butyl(phenyl)phosphanyl]-1-phenylethanamine
• CAS: 220812-79-3
• 化学式: C₁₈H₂₄NP
• 分子量: 285.369
• InChiKey: FIHQXQSCBNIZCF-OOJLDXBWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-(1-methylbenzyl)amino-tert-butylphenylphosphine 在 硼烷四氢呋喃络合物 作用下， 以 四氢呋喃 为溶剂， 以90%的产率得到(S)-(1-phenylethylamino)(tert-butyl)phenylphosphine borane complex
  参考文献：
  名称：

  Asymmetric synthesis of chiral N-(1-methylbenzyl)aminophosphines

  摘要：

  The reactions of chlorophosphines 1 with (S)- or (R)-1-methylbenzylamines 2 proceed stereoselectively to give N-(1-methylbenzyl)aminophosphines 3, which were isolated as crystalline borane complexes with 100% diastereomeric purity. The absolute configuration of the new chiral compounds was established by X-ray analysis and chemical extrapolation. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00750-4
• 作为产物：
  描述：

  (S)-(-)- α-甲基苄胺 、 tert-butylchlorophenylphosphane 在 三乙胺 作用下， 以 苯 为溶剂， 以85%的产率得到N-(1-methylbenzyl)amino-tert-butylphenylphosphine
  参考文献：
  名称：

  手性胺与外消旋氯膦的立体选择性反应

  摘要：

  外消旋氯膦与手性 l-苯乙胺或氨基酸酯发生立体选择性反应，得到富含非对映异构体的氨基膦 3，将其分离为非对映异构纯结晶硼烷配合物。氧化、硫化、与甲基碘的反应提供氨基膦的旋光衍生物。次膦酸酰胺的 (R,S)-和 (S,S)-立体异构体通过结晶和快速色谱法分离。研究了磷酸酰胺的立体化学性质。三价磷原子的不对称诱导机制被合理化。

  DOI：

  10.1080/10426500490459650

文献信息

• A practical method for N-alkylation of phosphinic (thio)amides with alcohols via transfer hydrogenation
  作者：Tanner C. Jankins、Zi-Yang Qin、Keary M. Engle

  DOI：10.1016/j.tet.2019.04.029

  日期：2019.6

  This manuscript describes a modular method for preparing N-alkyl phosphinic amides from primary or secondary alcohols and primary phosphinic amide (R1R2P = ONH2) nucleophiles via transfer hydrogenation. The transformation typically proceeds in excellent yields, employs conveniently available reagents, and produces water as the only byproduct.

  该手稿描述了通过转移氢化从伯或仲醇和伯次膦酰胺（R 1 R 2 P = ONH 2）亲核试剂制备N-烷基次膦酰胺的模块化方法。该转化通常以优异的收率进行，使用方便获得的试剂，并且产生水作为唯一的副产物。
• P-Chirogenic Diphosphazanes with Axially Chiral Substituents and Their Use in Rh-Catalyzed Asymmetric Hydrogenation
  作者：Jan-Ole Moritz、Soumyadeep Chakrabortty、Bernd H. Müller、Anke Spannenberg、Paul C. J. Kamer

  DOI：10.1021/acs.joc.0c01108

  日期：2020.11.20

  A convenient synthesis of enantiopure P-chirogenic diphosphazanes incorporating bulky bisphenol and 1,1′-bi-2-naphthol-derived substituents via the functionalization of a readily accessible enantiopure lithium phosphinoamide with chlorophosphoridites was developed. Since the product requires no subsequent deprotection, the protocol provides an easy, convenient synthesis of P-chirogenic ligands on the

  开发了一种方便的合成方法，该方法通过容易获得的对映纯纯膦酰氨基锂与氯代亚磷酸酯的官能化，结合了庞大的双酚和1,1'-联-2-萘酚衍生的对映体纯的手性二磷氮烷。由于产物不需要随后的脱保护，因此该方案以克规模提供了一种简便的P-产色配体的合成方法。将配体用于基准底物的Rh催化不对称氢化中，提供高达96％的对映体过量值。
• Stereochemistry of electrophilic and nucleophilic substitution at phosphorus
  作者：Oleg I. Kolodiazhnyi

  DOI：10.1080/10426507.2018.1521409

  日期：2019.5.27

  Abstract Stereochemistry and mechanisms of nucleophilic [SN2(P)] and electrophilic [SE2(P)} reactions have been analyzed, discussed and confirmed by experimental studies. SE2(P) reactions proceed with the retention of absolute configuration, while the SN2(P) reactions react with the inversion of the configuration at the phosphorus atom. GRAPHICAL ABSTRACT

  摘要 亲核[SN2(P)]和亲电[SE2(P)}反应的立体化学和机理已被实验研究分析、讨论和证实。SE2(P)反应在保留绝对构型的情况下进行，而SN2(P)反应在磷原子处发生构型反转。图形概要
• Stereoselective Reactions of Optically Active Derivatives of α-Methylbenzylaminophosphine
  作者：O. I. Kolodyazhnyi、N. V. Andrushko、E. V. Grishkun

  DOI：10.1023/b:rugc.0000031849.78207.1c

  日期：2004.4

  A number of N+(alpha-methylbenzyl) phosphorus amides were synthesized, and their stereochemical properties were studied. Reactions of achiral chlorophosphines with optically active alpha-methylbenzylamine are accompanied by asymmetric induction at the phosphorus atom to give optically active diastereoisomers of N-(alpha-methylbenzyl)aminophosphines, which were isolated as the corresponding borane complexes with 100% optical purity. Stereochemically pure (R,S)-aminophosphines were obtained by decomposition of these complexes via treatment with diethylamine. Their oxidation, sulfurization, and alkylation with methyl iodide afforded optically active aminophosphine derivatives. Hydrolysis of (R,S)-aminophosphines gave optically active tert-butylphenylphosphine oxide and phosphonic acid amides. (R,S)- and (S,S)-Diastereoisomers of N-(alpha-methylbenzyl)phosphinic amides were separated by crystallization and flash chromatography, and their absolute configuration was established. Also, derivatives of bis- and tris(alpha-methylbenzylamino)phosphines were synthesized.
• Synthesis of Chiral tert-Butylphenylphosphine Oxide
  作者：E. V. Grishkun、A. O. Kolodyazhnaya、O. I. Kolodyazhnyi

  DOI：10.1023/b:rugc.0000018664.98642.48

  日期：2003.11