2-(bis(3,5-dimethylphenyl)phosphino)-1,1'-binaphthyl | 701935-45-7

• 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: 2-(bis(3,5-dimethylphenyl)phosphino)-1,1'-binaphthyl
• 英文别名: bis(3,5-dimethylphenyl)-(1-naphthalen-1-ylnaphthalen-2-yl)phosphane
• CAS: 701935-45-7
• 化学式: C₃₆H₃₁P
• 分子量: 494.616
• InChiKey: FFRNGIWZRXFPDR-UHFFFAOYSA-N

物化性质

• 沸点：
  641.5±55.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  10.2
• 重原子数：
  37
• 可旋转键数：
  4
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  bis[(benzyldimethylamino)chloropalladium(II)] 、 2-(bis(3,5-dimethylphenyl)phosphino)-1,1'-binaphthyl 以 二氯甲烷 为溶剂， 以56%的产率得到[PdCl(C6H4CH2NMe2)(2-(bis(3,5-dimethylphenyl)phosphino)-1,1'-binaphthyl)]
  参考文献：
  名称：

  3,5-Dialkyl Effect on Enantioselectivity in Pd Chemistry:  Applications Involving Both Bidentate and Monodentate Auxiliaries

  摘要：

  The structural 3,5-dialkylphenyl effect on enantioselectivity is demonstrated for several Pd-catalyzed reactions including a ring-opening transmetalation, Heck arylation, and allylic alkylation. For these homogeneously catalyzed reactions the observed enantiomeric excesses (ee's) are found to improve by more than 15%. The ligands tested include MeO-Biphep and a P,N-phosphino-oxazoline-bidentate ligand containing 3,5-di-tert-butylphenyl substituents. Further, several derivatives of the monodentate auxiliary MOP ((R)-2-diarylphosphino-1,1'-binaphthyl) have been modified to include 3,5-dialkylphenyl substituents and these auxiliaries have been tested in Pd-catalyzed enantioselective hydrosilylation chemistry. For some, but not all of these MOP ligands, enhanced ee's of the order of 40-50% are found. Variable-temperature and 2-D NMR studies have been carried out on new model complexes and reveal selected restricted rotation around a number of the P-C(Ipso) aryl bonds. Solid-state structures for two of the new complexes, PdBr(p-NCC6H4)(phosphino-oxazoline, 2b), 8b, and PdCl(C6H4CH2NMe2)(MOP, 4b), 9b, have been determined.

  DOI：

  10.1021/om034381b
• 作为产物：
  描述：

  (S)-2-((trifluoromethanesulfonyl)oxy)-1,1'-binaphthyl 在 palladium diacetate 、 三氯硅烷 、 三乙胺 、 N,N-二异丙基乙胺 、 1,4-双(二苯基膦)丁烷 作用下， 以 二甲基亚砜 、 甲苯 为溶剂， 反应 39.0h， 生成 2-(bis(3,5-dimethylphenyl)phosphino)-1,1'-binaphthyl
  参考文献：
  名称：

  Modification of Chiral Monodentate Phosphine (MOP) Ligands for Palladium-Catalyzed Asymmetric Hydrosilylation of Styrenes

  摘要：

  在钯催化的苯乙烯与三氯硅烷的不对称氢化硅烷化反应中，研究了几种手性单膦配体 (R)-2-二芳基膦基-1,1'-联萘 (2) 的对映选择性。在与 (R)-2-双[3,5-双(三氟甲基)苯基]膦基-1,1'-联萘 (2g) 的反应中观察到最高的对映选择性，得到 98 的 (S)-1-苯基乙醇氢化硅烷化产物氧化后的％ee。

  DOI：

  10.1246/cl.2000.1272

文献信息

• [EN] IRIDIUM COMPLEX AND METHOD FOR PRODUCING OPTICALLY ACTIVE COMPOUND<br/>[FR] COMPLEXE D'IRIDIUM ET PROCÉDÉ POUR PRODUIRE UN COMPOSÉ OPTIQUEMENT ACTIF
  申请人：TAKASAGO PERFUMERY CO LTD

  公开号：WO2012029970A1

  公开（公告）日：2012-03-08

  An object of the present invention is to provide a novel iridium complex, and to provide a novel catalyst having excellent performances in terms of enantioselectivity, catalytic activity, and the like. Provided is an iridium complex of the following general formula (1): IrHZ2(PP)(Q)m (1) wherein Z represents a halogen atom, PP represents a bisphosphine, Q represents an amine, and m represents 1 or 2.

  本发明的目的是提供一种新型铱配合物，并提供一种在对映选择性、催化活性等方面具有优异性能的新型催化剂。提供的是下列一般式（1）的铱配合物：IrHZ2（PP）（Q）m（1），其中Z代表卤素原子，PP代表双膦，Q代表胺，m代表1或2。
• Compounds containing 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl and catalytic metal complexes thereof
  申请人：Takasago International Corporation

  公开号：EP0444930A1

  公开（公告）日：1991-09-04

  A phosphine compound 2,2′-bis[di-(3,5-dialkylphenyl) phosphino]-1,1′-binaphthyl is represented by the formula wherein R represents a C1-4 alkyl group. Synthesis is by reacting 2,2′-dibromo-1,1′-binaphthyl (see JP-A-55-61937) with Mg and reacting the resultant Grignard reagent with a bis(3,5-dialkyphenyl phosphonyl chloride;the resulting racemic phosphoryl binaphthyl is dissolved and crystals thereof recrystallised to purify them; (+)- and (-)- forms of the free phosphine oxide are obtained and reduced with trichlorosilane to provide the (+)- or (-)- isomers of the novel compound; or the racemate can be produced. The compound can be reacted with a compound of a transition element such as rhodium, palladium or ruthenium as a ligand to make a complex thereof which is useful as a catalyst in an asymmetric synthesis reaction, e.g. asymmetric hydrogenation of a β-keto ester, to give a product of high optical purity in high yield.

  一种 2,2′-双[二(3,5-二烷基苯基)膦]-1,1′-联萘的膦化合物由式表示 其中 R 代表 C1-4 烷基。 合成方法是将 2,2′-二溴-1,1′-联萘（见 JP-A-55-61937）与镁反应，并将生成的格氏试剂与双(3,5-二烷基苯基)膦酰氯反应；将生成的外消旋联萘膦酰氯溶解并重结晶以提纯；获得游离氧化膦的(+)-和(-)-形式，并用三氯硅烷还原，得到新型化合物的(+)-或(-)-异构体；或者生成外消旋体。 该化合物可作为配体与过渡元素（如铑、钯或钌）的化合物反应，制成其配合物，在不对称合成反应（如 β-酮酯的不对称氢化反应）中用作催化剂，从而高产率地得到高光学纯度的产物。
• Asymmetric Hydrosilylation of Styrenes Catalyzed by Palladium−MOP Complexes:  Ligand Modification and Mechanistic Studies
  作者：Tamio Hayashi、Seiji Hirate、Kenji Kitayama、Hayato Tsuji、Akira Torii、Yasuhiro Uozumi

  DOI：10.1021/jo001614p

  日期：2001.2.1

  In the palladium-catalyzed asymmetric hydrosilylation of styrene (3a) with trichlorosilane, several chiral monophosphine ligands, (R)-2-diarylphosphino-1,1'-binaphthyls(2a-g), were examined for their enantioselectivity. The highest enantioselectivity was observed in the reaction with (R)-2-bis [3,5-bis(trifluoromethyl)phenyl] phosphino-l,1'-binaphthyl (2g), which gave (S)-1-phenylethanol (5a) of 98% ee after oxidation of the hydrosilylation product, 1-phenyl-1-(trichlorosilyl)ethane (4a). The palladium complex of 2g also efficiently catalyzed the asymmetric hydrosilylation of substituted styrenes on the phenyl ring or at the beta position to give the corresponding chiral benzylic alcohols of over 96% ee. Deuterium-labeling studies on the hydrosilylation of regiospecifically deuterated styrene revealed that P-hydrogen elimination from l-phenylethyl(silyl)palladium intermediate is very fast compared with reductive elimination giving hydrosilylation product when ligand 2g is used. The reaction of o-allylstyrene (9) with trichlorosilane catalyzed by (R)-2g/Pd gave (1S,2R)-1-methyl-2-(trichlorosilylmethyl)indan (10) (91% ee) and (S)-1-(2-(propenyl)phenyl)-1-trichlorosilylethanes (11a and 11b) (95% ee). On the basis of their opposite configurations at the benzylic position, a rationale for the high enantioselectivity of ligand 2g is proposed.
• METAL COMPLEXES FOR USE IN THE CARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS
  申请人：Lucite International UK Limited

  公开号：EP2007703A1

  公开（公告）日：2008-12-31
• IRIDIUM COMPLEX AND METHOD FOR PRODUCING OPTICALLY ACTIVE COMPOUND
  申请人：Takasago International Corporation

  公开号：EP2611819A1

  公开（公告）日：2013-07-10