(R)-3-methyl-2,2'-bis(methoxy(methoxy))-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)-3-methyl-2,2'-bis(methoxy(methoxy))-1,1'-binaphthyl
• 英文别名: (R)-2,2'-bis(methoxymethoxy)-3'-methyl-1,1'-binaphthyl；2,2'-Bis(methoxymethoxy)-3-methyl-1,1'-binaphthyl；2-(methoxymethoxy)-1-[2-(methoxymethoxy)naphthalen-1-yl]-3-methylnaphthalene
• 化学式: C₂₅H₂₄O₄
• 分子量: 388.463
• InChiKey: AKVXMDYTJRKDHV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  29
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R)-3-methyl-2,2'-bis(methoxy(methoxy))-1,1'-binaphthyl 在 copper(l) iodide 、 四(三苯基膦)钯 、 叔丁基锂 、 三乙胺 作用下， 以 四氢呋喃 、 苯 为溶剂， 生成 o-phenylenebis(3-ethynyl-2,2'-bis(methoxy(methoxy))-3'-methyl-1,1'-binaphthyl)
  参考文献：
  名称：

  Phenylenebis(ethynyl)-Tethered Bis-BINOL Ligands for Enantioselective Catalyst Based on Dimeric Ti(IV) Aggregate

  摘要：

  [GRAPHICS]Bis-BINOLs 7a-c in which two BINOL units are tethered by phenylenebis(ethynyl) groups react with titanium tetraisopropoxide (2 equiv) to form intramolecular dimeric titanium(IV) aggregates 2a-c. Of these, 2a,b with an o-phenylenebis(ethynyl) tether are stable in the presence of excess titanium tetraisopropoxide. Complex 2a exhibits a relatively high enantioselectivity in asymmetric addition of diethylzinc to an aldehyde.

  DOI：

  10.1021/ol0360546
• 作为产物：
  描述：

  (R)-(+)-2,2’-双(甲氧基甲氧基)-1,1’-联萘 、 碘甲烷 在 叔丁基锂 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 以56%的产率得到(R)-3-methyl-2,2'-bis(methoxy(methoxy))-1,1'-binaphthyl
  参考文献：
  名称：

  3-取代的不对称BINOL的高活性钛配合物催化的醛的对映选择性烷基化。

  摘要：

  [反应：见正文]衍生自3-（3,5-二苯基苯基）-BINOL的钛络合物在醛的不对称烷基化反应中表现出增强的催化活性，使催化剂用量减少至小于1 mol％，而不会降低催化剂的质量。对映选择性。

  DOI：

  10.1021/ol061407x

文献信息

• Enantioselective Alkylation of Aldehydes Catalyzed by a Highly Active Titanium Complex of 3-Substituted Unsymmetric BINOL
  作者：Toshiro Harada、Kousou Kanda

  DOI：10.1021/ol061407x

  日期：2006.8.1

  [reaction: see text] A titanium complex derived from 3-(3,5-diphenylphenyl)-BINOL exhibits an enhanced catalytic activity in the asymmetric alkylation of aldehydes, allowing the reduction of the catalyst amount to less than 1 mol % without deterioration in enantioselectivity.

  [反应：见正文]衍生自3-（3,5-二苯基苯基）-BINOL的钛络合物在醛的不对称烷基化反应中表现出增强的催化活性，使催化剂用量减少至小于1 mol％，而不会降低催化剂的质量。对映选择性。
• Syntheses and Applications of 2-Phosphino-2‘-alkoxy-1,1‘-binaphthyl Ligands. Development of a Working Model for Asymmetric Induction in Hydrovinylation Reactions
  作者：Biswajit Saha、T. V. RajanBabu

  DOI：10.1021/jo062044h

  日期：2007.3.1

  Among the handful of monophosphine ligands that effect asymmetric hydrovinylation of vinylarenes, 2-diphenylphosphino-2‘-methoxy-1,1‘-binaphthyl (MOP) is among the most accessible. Addition of a methyl group at the 3‘-position of this ligand significantly improves the enantioselectivity of hydrovinylation of prototypical alkenes. Introduction of a chiral phospholane at the C2 position of this scaffolding

  在影响乙烯基芳烃不对称氢乙烯基化的少数单膦配体中，最容易获得的是2-二苯基膦基2'-甲氧基-1,1'-联萘基（MOP）。在该配体的3'-位处添加甲基显着改善了原型烯烃的水乙烯基化的对映选择性。在该支架的C 2位置引入手性磷杂环戊烯对对映选择性没有影响。这些结果与针对该严格反应的不对称诱导所提出的模型是一致的。
• Expedient route to 3- and 3,3′-substituted 1,1′-bi-2-naphthols by directed ortho metalation and suzuki cross coupling methods
  作者：Paul J. Cox、Wei Wang、Victor Snieckus

  DOI：10.1016/s0040-4039(00)74182-7

  日期：1992.4

  A directed ortho metalation-based route to 3- and 3,3'-substituted binaphthols 2a-c and 3a-c, including chiral materials, is described. Using the Suzuki cross coupling process, dibromo system 3a (E = Br) has been transformed into 3,3'-diaryl binaphthols 5.
• A Mechanistic Investigation of the Asymmetric Meerwein−Schmidt−Ponndorf−Verley Reduction Catalyzed by BINOL/AlMe₃Structure, Kinetics, and Enantioselectivity
  作者：Christopher R. Graves、Hongying Zhou、Charlotte L. Stern、SonBinh T. Nguyen

  DOI：10.1021/jo070563u

  日期：2007.11.1

  [Graphics]The kinetics of the Al-catalyzed asymmetric Meerwein-Schmidt-Ponndorf-Verley (MSPV) reduction are presented. Structural identification of the catalytic precursor formed in situ between (S)-2,2'-dihydroxy-1,1'-binapthyl ((S)-BINOL), AlMe3, and 2-propanol was established through H-1 and Al-27 NMR spectroscopies, and APCIMS. All experimental evidence points toward the formation of a BINOL-chelated, pentacoordinate aluminum species in solution. Ligand-accelerated catalysis was confirmed for the phenol ate/AlMe3/2-propanol system. The rate law for the catalytic reaction was determined to be nearly unimolecular dependent on aluminum, zero-order dependent on substrate, and inversely dependent on 2-propanol. At the low catalyst loading employed in the BINOL/AlMe3 system, the inherent reversibility of the MSPV reaction does not affect product yield or enantiomeric excess over time. Systematic ligand studies imply that while a tetrahedral geometry around the aluminum center may result in the most active MSPV reduction catalysts, the enantioselectivity of the reaction is enhanced when the aluminum center allows for a 2-point coordination of the substrate to achieve a pentacoordinate geometry with the fifth ligand weakly coordinated to the axial site of a pseudo square pyramid.
• Phenylenebis(ethynyl)-Tethered Bis-BINOL Ligands for Enantioselective Catalyst Based on Dimeric Ti(IV) Aggregate
  作者：Toshiro Harada、Yuki Hiraoka、Takahiro Kusukawa、Yasuhisa Marutani、Shinichiro Matsui、Masashi Nakatsugawa、Koso Kanda

  DOI：10.1021/ol0360546

  日期：2003.12.1

  [GRAPHICS]Bis-BINOLs 7a-c in which two BINOL units are tethered by phenylenebis(ethynyl) groups react with titanium tetraisopropoxide (2 equiv) to form intramolecular dimeric titanium(IV) aggregates 2a-c. Of these, 2a,b with an o-phenylenebis(ethynyl) tether are stable in the presence of excess titanium tetraisopropoxide. Complex 2a exhibits a relatively high enantioselectivity in asymmetric addition of diethylzinc to an aldehyde.