(S_P,S)-N-(1-methylbenzyl)amino-tert-butylphenylphosphine

• 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: (S_P,S)-N-(1-methylbenzyl)amino-tert-butylphenylphosphine
• 英文别名: (SP,S)-tert-butyl(α-methylbenzylamino)phenylphosphine；(S_P,S)-N-(1-phenylethyl)amino-tert-butylphenylphosphine；(1S)-N-[tert-butyl(phenyl)phosphanyl]-1-phenylethanamine
• 化学式: C₁₈H₂₄NP
• 分子量: 285.369
• InChiKey: FIHQXQSCBNIZCF-MGPUTAFESA-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：

  硼烷 、 (S_P,S)-N-(1-methylbenzyl)amino-tert-butylphenylphosphine 以 四氢呋喃 为溶剂， 以80%的产率得到(S_P,S)-N-(1-phenylethyl)amino-tert-butylphenylphosphine borane complex
  参考文献：
  名称：

  Synthesis of Chiral tert-Butylphenylphosphine Oxide

  摘要：

  DOI：

  10.1023/b:rugc.0000018664.98642.48
• 作为产物：
  描述：

  N-(1-methylbenzyl)amino-tert-butylphenylphosphine 在 硼烷 、 二乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 22.0h， 生成 (S_P,S)-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

• 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。
• 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.
• Asymmetric synthesis of chiral N-(1-methylbenzyl)aminophosphines
  作者：Oleg I. Kolodiazhnyi、Evgenyi V. Gryshkun、Natalia V. Andrushko、Matthias Freytag、Peter G. Jones、Reinhard Schmutzler

  DOI：10.1016/s0957-4166(02)00750-4

  日期：2003.1

  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.
• 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
• STEREOSELECTIVE REACTIONS OF CHIRAL AMINES WITH RACEMIC CHLOROPHOSPHINES
  作者：Evgenyi V. Gryshkun、Natalia V. Andrushko、Oleg I. Kolodiazhnyi

  DOI：10.1080/10426500490459650

  日期：2004.6

  stereoselectively with chiral l-phenylethylamines or amino acid esters to give diastereomerically enriched aminophosphines 3, which were isolated as diastereomerically pure crystalline borane complexes. Oxidation, thionation, the reaction with methyl iodide provide optically active derivatives of aminophosphines. (R,S)- and (S,S)-stereomers of phosphinic acid amides were separated by crystallization and a flash-chromatography

  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。