(R)-2-(dicyclohexylphosphino)-2'-benzyloxy-1,1'-binaphthyl

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (R)-2-(dicyclohexylphosphino)-2'-benzyloxy-1,1'-binaphthyl
• 英文别名: Dicyclohexyl-[1-(2-phenylmethoxynaphthalen-1-yl)naphthalen-2-yl]phosphane
• 化学式: C₃₉H₄₁OP
• 分子量: 556.728
• InChiKey: PQJLQJHNAVCHEJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.7
• 重原子数：
  41
• 可旋转键数：
  7
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  氯代环己烷 在 1,1'-双(二苯基膦)二茂铁 、 三氯硅烷 、 碘 、 palladium diacetate 、 potassium carbonate 、 magnesium 、 三乙胺 、 N,N-二异丙基乙胺 、 sodium hydroxide 作用下， 以 1,4-二氧六环 、 N-甲基吡咯烷酮 、 甲醇 、 乙醚 、 水 、 丙酮 、 甲苯 为溶剂， 反应 128.66h， 生成 (R)-2-(dicyclohexylphosphino)-2'-benzyloxy-1,1'-binaphthyl
  参考文献：
  名称：

  酯烯醇化物的对映选择性分子间α-芳基化形成三级立体中心

  摘要：

  在过渡金属催化的羰基化合物的不对称α-芳基化中，由于单芳基化产物容易烯醇化，形成具有高对映选择性的三级中心是一个长期存在的问题。在此，我们报告了使用由新的 (R)-H(8)-BINOL 衍生的单膦支持的钯催化剂的示例。甲硅烷基乙烯酮缩醛与弱碱性活化剂一起用作酯阴离子的等价物，它们与芳基三氟甲磺酸酯以优异的对映体过量 (ee) 顺利反应。该反应的有效性在 92% ee 的 (S)-萘普生的克级合成中得到证明。

  DOI：

  10.1021/ja2066829

文献信息

• Hydroesterification of Vinylarenes Catalyzed by Palladium Complexes of Dialkylmonoaryl- and Monoalkyldiarylphosphines
  作者：Yasutoyo Kawashima、Kentaro Okano、Kyoko Nozaki、Tamejiro Hiyama

  DOI：10.1246/bcsj.77.347

  日期：2004.2

  Hydroesterification of vinylarenes using a mixture of PdCl2 and monodentate phosphorus ligands as a catalyst was studied. As ligands, menthyldiphenylphosphine (MDPP), neomenthyldiphenylphosphine (NMDPP), and dicyclohexyl(phenyl)phosphine (Cy2PPh) were effective to obtain branched esters with high regioselectivity under the moderate reaction conditions without additives such as acids. Not only electronic effects but also steric effects of the cycloalkyl groups were revealed to be significant in order to achieve high catalytic activity. When (S)-2-dicyclopentylphosphino-2′-methoxy-1,1′-binaphthyl was used for the asymmetric hydroesterification of 2-methoxy-6-vinylnaphthalene, (S)-naproxen methyl ester was obtained with 53% ee.

  研究了使用PdCl2和单齿磷配体混合物作为催化剂对乙烯基芳烃进行水解酯化反应。作为配体，薄荷基二苯基膦（MDPP）、新薄荷基二苯基膦（NMDPP）和二环己基（苯基）膦（Cy2PPh）在无酸等添加剂的温和反应条件下有效地产生了高区域选择性的支链酯。研究表明，环烷基基团的电子效应和立体效应在实现高催化活性方面均具有重要意义。当使用(S)-2-二环戊基膦-2'-甲氧基-1,1'-联萘进行2-甲氧基-6-乙烯基萘的非对称水解酯化时，得到了53%对映体过量(S)-萘普生甲酯。
• CHIRAL PHOSPHINES FOR PALLADIUM-CATALYZED ASYMMETRIC ALPHA-ARYLATION OF ESTER ENOLATES TO PRODUCE TERTIARY STEREOCENTERS IN HIGH ENANTIOSELECTIVITY
  申请人：Zhou Steve Jianrong

  公开号：US20150166586A1

  公开（公告）日：2015-06-18

  The disclosure provides new and improved methods for the Pd-catalyzed asymmetric α-arylation of ester compounds, which produce the corresponding α-aryl moiety in high enantioselectivity (generally >90% ee). The present methods utilize a palladium catalyst supported by new (R)—H 8 -BINOL-derived monophosphine ligands. The method is applicable to a wide variety of aryl triflate substrates having variations in both electronic and steric properties. These aryl triflate substrates react with various α-alkyl (Z)- and/or (E)-0-trimethylsilyl ketene acetals in the presence of a Pd catalyst, (R)—H 8 -BINOL-derived monophosphine ligand, and a mild activator, for example, LiOAC, to provide the asymmetric α-arylation of ester compounds in high ee.

  本公开提供了新的和改进的方法，用于Pd催化的酯化合物的不对称α-芳基化，可产生相应的α-芳基基团，并具有高对映选择性（通常> 90％ ee）。本方法利用由新（R）-H8-BINOL衍生的单膦配体支持的钯催化剂。该方法适用于具有电子和立体性质变化的各种芳基三氟甲烷底物。这些芳基三氟甲烷底物在Pd催化剂，（R）-H8-BINOL衍生的单膦配体和温和的活化剂（例如LiOAC）存在下，与各种α-烷基（Z）-和/或（E）-0-三甲基硅基乙酮缩醛反应，从而提供高对映选择性的酯化合物的不对称α-芳基化。
• Synthesis of Bulky and Electron-Rich MOP-type Ligands and Their Applications in Palladium-Catalyzed C−N Bond Formation
  作者：Xiaomin Xie、Tony Y. Zhang、Zhaoguo Zhang

  DOI：10.1021/jo060945k

  日期：2006.8.1

  A series of 2-dialkylphosphino-2'-alkoxy-1,1'-binaphthyl ligands ( 6a-c and 8a-c) have been prepared conveniently by a lithium-initiated ring-opening reaction of dinaphthofuran, followed by selective phosphorylation. These compounds displayed a remarkable air and moisture stability, both in solid form and in solution. Application of these phosphine ligands in palladium-catalyzed C-N bond forming reactions revealed the crucial roles of the steric bulk of the substituents on the phosphorus atom governing the catalytic activity. Specifically, 2-di-tert-butylphosphino-2'-isopropoxy-1, 1'-binaphthyl ( 8b) proved to be the most effective for the aminations of aryl halides with primary amines, while the less bulky 2-dicyclohexyl-2'-methoxy-1,1'-binaphthyl ( 6a) was more effective for the aminations with secondary amines. The steric and electronic effects of the ligands were analyzed to account for these observations.
• [EN] CHIRAL PHOSPHINES FOR PALLADIUM-CATALYZED ASYMMETRIC ALPHA-ARYLATION OF ESTER ENOLATES TO PRODUCE TERTIARY STEREOCENTERS IN HIGH ENANTIOSELECTIVITY<br/>[FR] PHOSPHINES CHIRALES POUR L'ALPHA-ARYLATION ASYMÉTRIQUE CATALYSÉE PAR LE PALLADIUM DES ÉNOLATES D'ESTER POUR OBTENIR DES STÉRÉOCENTRES TERTIAIRES À UNE ÉNANTIOSÉLECTIVITÉ ÉLEVÉE
  申请人：UNIV NANYANG TECH

  公开号：WO2013028132A9

  公开（公告）日：2013-08-22
• US9512155B2
  申请人：——

  公开号：US9512155B2

  公开（公告）日：2016-12-06