(S)-(+)-(2-Methoxy-1-naphthyl)methylphenylphosphine oxide | 103078-89-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (S)-(+)-(2-Methoxy-1-naphthyl)methylphenylphosphine oxide
• 英文别名: (S_P*)-methyl-(2-methoxy-1-naphthyl)phenylphosphine oxide；(S)-2-methoxy-1-(methyl-phenyl-phosphinoyl)naphthalene；2-Methoxy-1-[methyl(phenyl)phosphoryl]naphthalene
• CAS: 103078-89-3
• 化学式: C₁₈H₁₇O₂P
• 分子量: 296.306
• InChiKey: MUKAWZDZFFGBDD-NRFANRHFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S)-(+)-(2-Methoxy-1-naphthyl)methylphenylphosphine oxide 在 三氯硅烷 、 三乙胺 作用下， 以 苯 为溶剂， 反应 0.75h， 生成 (R)-(+)-(2-Methoxy-1-naphthyl)methylphenylphosphine 、 (S)-(-)-(2-Methoxy-1-naphthyl)methylphenylphosphine
  参考文献：
  名称：

  Kinetic Resolution of Phosphines and Phosphine Oxides with Phosphorus Stereocenters by Hydrolases

  摘要：

  Lipase from Candida rugosa (CRL) and cholesterol esterase (CE) catalyzed the enantioselective hydrolysis of pendant acetates in chiral phosphines and phosphine oxides. The enantioselectivity for most substrates was modest (E = 1.5-4.8), but both hydrolases showed high enantioselectivity for one substrate, ArPhMeP=O (Ar = 1-(2-acetoxy)naphthyl, 4c), E = 81 (CRL) and 32 (GE). Preparative-scale resolution of (+/-)-4c (1.0 g) catalyzed by CRL yielded enantiomerically-enriched starting acetate, (S)-(+)-4c, 0.48 g, 90% ee as well as product alcohol, (R)(-)-4b (Ar = 1-(2-hydroxy)naphthyl), 0.39 g, 88% se. Recrystallization of 4b from toluene raised the enantiomeric purity to >95% ee. Standard chemical steps followed by stereospecific reduction gave both enantiomers of phosphine ArPhMeP (Ar = 1-(2-methoxy)naphthyl) with 96-97% ee. This phosphine is an analog of PAMP (Ar = 2-methoxyphenyl), a chiral phosphine used in asymmetric synthesis.

  DOI：

  10.1021/jo00104a015
• 作为产物：
  描述：

  (S)-(+)-(2-Acetoxy-1-naphthyl)methylphenylphosphine oxide 在 sodium hydroxide 、 potassium carbonate 作用下， 以 甲醇 、 丙酮 为溶剂， 反应 1.0h， 生成 (S)-(+)-(2-Methoxy-1-naphthyl)methylphenylphosphine oxide
  参考文献：
  名称：

  Kinetic Resolution of Phosphines and Phosphine Oxides with Phosphorus Stereocenters by Hydrolases

  摘要：

  Lipase from Candida rugosa (CRL) and cholesterol esterase (CE) catalyzed the enantioselective hydrolysis of pendant acetates in chiral phosphines and phosphine oxides. The enantioselectivity for most substrates was modest (E = 1.5-4.8), but both hydrolases showed high enantioselectivity for one substrate, ArPhMeP=O (Ar = 1-(2-acetoxy)naphthyl, 4c), E = 81 (CRL) and 32 (GE). Preparative-scale resolution of (+/-)-4c (1.0 g) catalyzed by CRL yielded enantiomerically-enriched starting acetate, (S)-(+)-4c, 0.48 g, 90% ee as well as product alcohol, (R)(-)-4b (Ar = 1-(2-hydroxy)naphthyl), 0.39 g, 88% se. Recrystallization of 4b from toluene raised the enantiomeric purity to >95% ee. Standard chemical steps followed by stereospecific reduction gave both enantiomers of phosphine ArPhMeP (Ar = 1-(2-methoxy)naphthyl) with 96-97% ee. This phosphine is an analog of PAMP (Ar = 2-methoxyphenyl), a chiral phosphine used in asymmetric synthesis.

  DOI：

  10.1021/jo00104a015

文献信息

• [EN] METHOD FOR INCREASING THE ENANTIOMERIC EXCESS OF CHIRAL PHOSPHINE OXIDES, SULPHIDES, IMIDES AND BORANES<br/>[FR] PROCÉDÉ POUR AUGMENTER L'EXCÈS ÉNANTIOMÉRIQUE DES OXYDES, DES SULFURES, ET DES IMIDES DE PHOSPHINE AINSI QUE DES PHOSPHINE-BORANES CHIRAUX
  申请人：CELTIC CATALYSTS LTD

  公开号：WO2010004278A1

  公开（公告）日：2010-01-14

  The present invention relates to a method for increasing the enantiomeric excess of a chiral phosphine oxide, a chiral phosphine sulphide, a chiral phosphine-borane and a chiral phosphine imide said method comprising the steps of: (a) contacting said chiral phosphine oxide, sulphide, imide or borane with a solvent to form a slurry; (b) partitioning the phosphine oxide, sulphide, imide or borane either into the solvent or as an insoluble product; and (c) optionally, isolating the partitioned phosphine oxide, sulphide, imide or borane.

  本发明涉及一种用于增加手性亚磷酰氧化物、手性亚磷酰硫、手性亚磷酰-硼烷和手性亚磷酰亚胺的对映体过量值的方法，所述方法包括以下步骤：(a)将所述手性亚磷酰氧化物、硫、亚胺或硼烷与溶剂接触以形成悬浮液；(b)将亚磷酰氧化物、硫、亚胺或硼烷分配到溶剂中或作为不溶产物；以及(c)可选地，分离出分配的亚磷酰氧化物、硫、亚胺或硼烷。
• A Simple Resolution Procedure Using the Staudinger Reaction for the Preparation of <i>P</i>-Stereogenic Phosphine Oxides
  作者：Neil G. Andersen、Philip D. Ramsden、Daqing Che、Masood Parvez、Brian A. Keay

  DOI：10.1021/jo015909u

  日期：2001.11.1

  (+/-)-P-stereogenic phosphines is achieved by exploiting the Staudinger reaction of a (+/-)-phosphine with enantiopure (1S,2R)-O-(tert-butyldimethylsilyl)isobornyl-10-sulfonyl azide. The resulting mixtures of diastereomeric phosphinimines are generally separable by fractional crystallization or flash chromatography. Subsequent acid-catalyzed hydrolysis provides the corresponding optically pure phosphine oxides

  通过利用（+/-）膦与对映纯（1S，2R）-O-（叔丁基二甲基甲硅烷基）异冰片基-10的Staudinger反应可实现多种（+/-）-P-立体异构膦的拆分-磺酰叠氮化物。非对映体膦亚胺的所得混合物通常可通过分步结晶或快速色谱分离。随后的酸催化的水解以高收率提供了相应的光学纯的氧化膦。
• Kinetic Resolution of Phosphines and Phosphine Oxides with Phosphorus Stereocenters by Hydrolases
  作者：Alessio N. Serreqi、Romas J. Kazlauskas

  DOI：10.1021/jo00104a015

  日期：1994.12

  Lipase from Candida rugosa (CRL) and cholesterol esterase (CE) catalyzed the enantioselective hydrolysis of pendant acetates in chiral phosphines and phosphine oxides. The enantioselectivity for most substrates was modest (E = 1.5-4.8), but both hydrolases showed high enantioselectivity for one substrate, ArPhMeP=O (Ar = 1-(2-acetoxy)naphthyl, 4c), E = 81 (CRL) and 32 (GE). Preparative-scale resolution of (+/-)-4c (1.0 g) catalyzed by CRL yielded enantiomerically-enriched starting acetate, (S)-(+)-4c, 0.48 g, 90% ee as well as product alcohol, (R)(-)-4b (Ar = 1-(2-hydroxy)naphthyl), 0.39 g, 88% se. Recrystallization of 4b from toluene raised the enantiomeric purity to >95% ee. Standard chemical steps followed by stereospecific reduction gave both enantiomers of phosphine ArPhMeP (Ar = 1-(2-methoxy)naphthyl) with 96-97% ee. This phosphine is an analog of PAMP (Ar = 2-methoxyphenyl), a chiral phosphine used in asymmetric synthesis.