methyl (R)-(-)-(2-methoxyphenyl)phenylphosphinite borane complex | 131740-16-4

• 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: methyl (R)-(-)-(2-methoxyphenyl)phenylphosphinite borane complex
• 英文别名: (+)-(R)-borane methoxy(2-methoxyphenyl)(phenyl)phosphane；(R)-methoxy(2-methoxyphenyl)phenylphosphane-borane (1/1)；(R)-(-)-[O-methyl (o-anisyl)phenylphosphinite]-borane；methyl (R)-(o-anisyl)phenylphosphinite-borane
• CAS: 131740-16-4
• 化学式: C₁₄H₁₈BO₂P
• 分子量: 260.08
• InChiKey: INUSSZXNUKWDEV-GOSISDBHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.97
• 重原子数：
  18.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.142
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  methyl (R)-(-)-(2-methoxyphenyl)phenylphosphinite borane complex 在 三乙烯二胺 、 正丁基锂 、 四甲基乙二胺 作用下， 以 乙醚 、 正己烷 为溶剂， 生成 Rel-(1R,1'S)-(9,9-dimethyl-9H-xanthene-4,5-diyl)bis((2-methoxyphenyl)(phenyl)phosphane)
  参考文献：
  名称：

  P-深生黄药磷配体及相关醚二膦类化合物的合成及在铑催化的不对称加氢中的应用

  摘要：

  通过完善的Jugé方法的改进，已经合成了一系列的P-手性黄原磷配体和相关的二芳基醚二膦。该方法包括在进行P-C偶联之前，对基于手性麻黄碱的次膦酸酯进行原位脱硼化处理。评价了在合成，长时间存储和催化应用过程中二膦的立体中心的立体化学完整性。在铑催化的异佛尔酮的不对称氢化反应中，作为工业上与之相关的具有二膦基化合物的孕甾烯酮的模型底物，可以实现几乎完全的转化，高的化学选择性和96％的ee。

  DOI：

  10.1021/acscatal.7b01260
• 作为产物：
  描述：

  (1R,2S)-2-{[(S)-(2-methoxyphenyl)phenylphosphanyl](methyl)amino}-1-phenylpropan-1-ol P-borane complex 在 H₂SO₄ 作用下， 以 甲醇 为溶剂， 以97%的产率得到methyl (R)-(-)-(2-methoxyphenyl)phenylphosphinite borane complex
  参考文献：
  名称：

  Formation of Diastereoisomerically Pure Oxazaphospholes and Their Reaction to Chiral Phosphane-Borane Adducts

  摘要：

  Starting with achiral phosphines and (1S,2S)-2-(methylamino)-1-phenylpropan-1-ol ((+)-pseudoephedrine) or (1R,2S)-2-(methylamino)-1-phenylpropan-1-ol ((-)-ephedrine), as chiral auxiliaries, diastereoisomerically pure oxazaphospholes wore prepared (Scheme 1). The configuration at the P-atom is controlled by the configuration at the Ph-substituted C(1) of (+)-pseudoephedrine or (-)-ephedrine, respectively. This was confirmed by X-ray crystal-structure analyses of two intermediate compounds in the synthesis route to the chiral triarylborane-phosphane adducts.

  DOI：

  10.1002/(sici)1522-2675(20000216)83:2<311::aid-hlca311>3.0.co;2-i

文献信息

• Stereodivergent S_N2@P Reactions of Borane Oxazaphospholidines: Experimental and Theoretical Studies
  作者：Hester Zijlstra、Thierry León、Abel de Cózar、Célia Fonseca Guerra、Daniel Byrom、Antoni Riera、Xavier Verdaguer、F. Matthias Bickelhaupt

  DOI：10.1021/ja400208t

  日期：2013.3.20

  with alkyl lithium reagents is reported. N-H oxazaphospholidines derived from both (+)-cis-1-amino-2-indanol and (-)-norephedrine provide inversion products in a highly stereoselective process. In contrast, N-Me oxazaphospholidines yield ring-opening products with retention of configuration at the P center, as previously reported by Jugé and co-workers. As a result, from a single amino alcohol auxiliary

  报道了 2-苯基 oxazaphosphollides 与烷基锂试剂的立体发散开环。源自 (+)-cis-1-amino-2-indanol 和 (-)-norrephedrine 的 NH oxazaphospholidines 在高度立体选择性过程中提供转化产物。相比之下，如 Jugé 及其同事先前报道的那样，N-Me oxazaphospholidines 产生开环产物，在 P 中心保留构型。因此，从单一的氨基醇助剂中，可以合成关键 P 立体中间体的两种对映异构体。在 DFT 水平上用模型 oxazaphospholidines 开环的理论研究阐明了这个过程的立体化学过程。NH 底物通过优先的背面 S(N)2@P 取代与磷反转，一步反应。N-甲基化底物优先通过两步前端 S(N)2@P 反应，产生开环产物，其中亲核甲基与 P 结合并保留构型。DFT 计算表明，BH3 单元是一个有效的导
• New P-chirogenic tert.-butyl-xantphos ligands and their application in asymmetric hydrogenation and alkylation
  作者：Jens Holz、Gudrun Wenzel、Anke Spannenberg、Mark Gandelman、Armin Börner

  DOI：10.1016/j.tet.2020.131142

  日期：2020.4

  of a broad library of new P-chirogenic Xantphos ligands is reported. A special feature is 2,7-di-tert.-butyl substituents in the backbone which requires the modification of the original synthetic approach. In comparison to related ligands reported formerly the substitution has a considerable influence on the results (yield and % e.e.) of metal catalyzed reactions, e.g. asymmetric rhodium catalyzed hydrogenation

  报道了合成新的P-手性Xantphos配体的广泛文库。比较特别的是2,7-二-叔-在需要原来的合成方法的变形例的主链丁基的取代基。与先前报道的相关配体相比，取代对金属催化反应的结果（产率和％ee）有很大影响，例如分别由不对称铑催化的异佛尔酮氢化和钯催化的烷基化。
• P-CHIRAL PHOSPHINE LIGANDS AND USE THEREOF FOR ASYMMETRIC SYNTHESIS
  申请人：BASF SE

  公开号：US20190211040A1

  公开（公告）日：2019-07-11

  The present invention relates to chiral compounds with two optically active phosphorus atoms, chiral transition metal catalysts which comprise these compounds as ligands, a process for preparing the P-chiral compounds and processes for asymmetric synthesis using the chiral transition metal catalysts. The present invention specifically relates to a process for preparing an optically active carbonyl compound by asymmetric hydrogenation of a prochiral α,β-unsaturated carbonyl compound with hydrogen in the presence of an optically active transition metal catalyst according to the invention. Yet more specifically, the present invention relates to a process for the asymmetric hydrogenation of citral, and also a process for preparing optically active menthol.

  本发明涉及具有两个光学活性磷原子的手性化合物，包括这些化合物作为配体的手性过渡金属催化剂，制备P-手性化合物的方法以及利用手性过渡金属催化剂进行不对称合成的方法。本发明具体涉及一种通过在本发明的光学活性过渡金属催化剂存在下，利用氢不对称氢化一种丙烯基α，β-不饱和羰基化合物制备光学活性羰基化合物的方法。更具体地说，本发明涉及柠檬醛的不对称氢化方法，以及制备光学活性薄荷醇的方法。
• Ferrocenyl Diphosphines Containing Stereogenic Phosphorus Atoms. Synthesis and Application in the Rhodium-Catalyzed Asymmetric Hydrogenation
  作者：Francesca Maienza、Michael Wörle、Pascal Steffanut、Antonio Mezzetti、Felix Spindler

  DOI：10.1021/om980754a

  日期：1999.3.1

  Enantiomerically pure (R)-2-methoxyphenyl(phenyl)-O-methylphosphinite borane (1a) and (R)-1-naphthyl(phenyl)-O-methylphosphinite borane (1b) react with 1,1‘-dilithioferrocene to give (S,S)-1,1‘-bis(2-methoxyphenyl(phenyl)phosphino)ferrocene borane (2a) and (S,S)-1,1‘-bis(1-naphthyl(phenyl)phosphino)ferrocene borane (2b). Deboranation with morpholine yields the diphosphines (S,S)-1,1‘-bis(2-methoxyphen

  对映体纯的（R）-2-甲氧基苯基（苯基）-O-甲基次膦酸酯硼烷（1a）和（R -1--1-萘基（苯基）-O-甲基次膦酸酯硼烷（1b）与1,1'-二硫代二茂铁反应S，S）-1,1'-双（2-甲氧基苯基（苯基）膦基）二茂铁硼烷（2a）和（S，S）-1,1'-双（1-萘基（苯基）膦基）二茂铁硼烷（2b）。用吗啉进行脱硼烷反应生成二膦（S，S）-1,1'-双（2-甲氧基苯基（苯基）膦基）二茂铁（3a）和（S，S）-1,1'-双（1-萘基（苯基） ）膦基二茂铁（图3b）以高产率和高diastereo-和对映体纯度，所确定的对应的氧化膦4一，b。X射线研究支持2a的（S，S）构型，并公开了3a在铂衍生物[PtCl 2（3a）]（5a）中的配位性能。铑（I）衍生物[Rh（COD）（3 a，b）] BF 4（6 a，b）已在各种烯烃和酮的对映选择性催化加氢中进行了制备和测试。在具有6a（97％ee）的（Z）-α
• Chemo-, regio- and stereoselective conversion of P-chirogenic phosphorus borane complexes into their PO or PS derivatives
  作者：Jacques Uziel、Christophe Darcel、Dominique Moulin、Christophe Bauduin、Sylvain Jugé

  DOI：10.1016/s0957-4166(01)00236-1

  日期：2001.6

  Chiral and achiral organophosphorus borane complexes are readily transformed into their corresponding phosphoryl or thiophosphoryl compounds in high yields using one-pot procedures with stereoselectivities reaching 100% in many cases. Both oxidation and sulfuration were performed under neutral or mild conditions and were applied to various organophosphorus borane complexes (phosphines, phosphinates, chlorophosphines, aminophosphines, etc.). In the case of the dissymmetric diphosphine or aminophosphine phosphinite ligands, the reaction of their diborane complexes proceeds regiospecifically to a single phosphorus group, affording the corresponding hybrid derivatives. (C) 2001 Elsevier Science Ltd. All rights reserved.