(R)-2,2'-dichloromethyl-1,1'-binaphthyl | 96693-27-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (R)-2,2'-dichloromethyl-1,1'-binaphthyl
• 英文别名: (R)-(+)-2,2'-bis(chloromethyl)-1,1'-binaphthalene；(+)-(R)-2,2'-bis(chloromethyl)-1,1'-binaphthyl；(R)-2,2'-bis chloromethyl-1,1'-binaphthyl；2,2'-bis(chloromethyl)-1,1'-binaphthalene；2,2'-bis(chloromethyl)-1,1'-binaphthyl；bis(2-chloromethyl)-1,1'-binaphthalene；2-(chloromethyl)-1-[2-(chloromethyl)naphthalen-1-yl]naphthalene
• CAS: 96693-27-5
• 化学式: C₂₂H₁₆Cl₂
• 分子量: 351.275
• InChiKey: OYVOPWAGYAKJAZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.09
• 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：

  (R)-2,2'-dichloromethyl-1,1'-binaphthyl 在 selenium 、 sodium tetrahydroborate 作用下， 以 乙醇 为溶剂， 反应 0.5h， 以80%的产率得到(R)-4,5-dihydro-3H-dinaphtho-[2,1-c:1',2'-e]-selenepin
  参考文献：
  名称：

  Synthesis of (R)-4,5-Dihydro-3H-Dinaphtho-[2,1-c:1',2'-e]Selenepin Oxide and Preliminary Studies on Its Use in the Oxidation of Sulfides

  摘要：

  The first synthesis (R)-4,5-dihydro-3H-dinaphtho-[2,1-c:1',2'-e]-selenepin oxide 1 has been achieved from (R)-(+)-1,1'-bi-2-naphthol, which in turn was obtained by resolution of rac-1,1'-bi-2-naphthol. Palladium catalyzed alkoxy-carbonylation of ditriflate 4 gave dimethyl eater 5 which was then reduced and the resultant diol converted to key intermediate chloride 8. Cyclization with sodium selenolate gave novel enantiomerically pure selenide 9, which upon oxidation yielded the desired selenoxide (R)-1. Preliminary studies on the oxidation of sulfides to sulfoxides using 1 and 2,2,2-trifluoroethane sulfonic acid are also described.

  DOI：

  10.1080/00397910008087448
• 作为产物：
  描述：

  S-1,1'-联-2-萘酚 在 三氯化硼 、 caesium carbonate 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 25.0h， 生成 (R)-2,2'-dichloromethyl-1,1'-binaphthyl
  参考文献：
  名称：

  威廉姆森反应：2,2'-双（溴甲基）-1,1'-联萘和1,1'-萘2,2'-二醇的交替拆分新方法。

  摘要：

  1,1'-联萘-2,2'-二醇（+）-（R）-1处理2,2'-双（溴甲基）-1,1'-联萘[[R，S）-2]和碳酸铯或碳酸钾在回流的丙酮中，制得非对映异构体二氧杂环烷酮（-）-（R，S）-3a和（+）-（R，R）-3b，以及环状四醚（+） -（R，R，R，S）-4作为分离的副产物。用三硼化硼促进的3a和3b裂解，分别得到光学纯的（-）-（S）-2和（+）-（R）-2，以及回收的二醇（+）-（R）-1。或者，相同的反应顺序也提供了从（R，S）-1和（+）-（R）-2分离出的二醇（-）-（S）-1和（+）-（R）-1通过使用三氯化硼进行醚裂解，从外消旋二溴化物（R，S）-2中得到光学纯的2,2'-双（氯甲基）-1,1'-联萘基（+）-（R）-5。

  DOI：

  10.1021/jo952011u

文献信息

• Matching and Mismatching Effects of Hybrid Chiral Biaxial Bisphosphine Ligands in Enantioselective Hydrogenation of Ketoesters
  作者：Xianfeng Sun、Wei Li、Le Zhou、Xumu Zhang

  DOI：10.1002/chem.200900722

  日期：2009.7.27

  Highly enantioselective hydrogenation reactions provide facile access to optically active α‐ and β‐hydroxy acid derivatives (see scheme), which are very important chiral building blocks for the syntheses of a variety of natural products and biologically active molecules. The selectivity data revealed that the matched ligand system was L*, which afforded much higher enantioselectivities in hydrogenation

  高度对映选择性的氢化反应可轻松获得旋光性α-和β-羟基酸衍生物（请参阅方案），这对于合成各种天然产物和具有生物活性的分子而言是非常重要的手性构建基。选择性数据表明，匹配的配体系统为L *，在β-酮酸酯和苯甲酰基甲酸甲酯的氢化反应中具有更高的对映选择性。
• Palladium-bisimidazol-2-ylidene complexes as catalysts for general and efficient Suzuki cross-coupling reactions of aryl chlorides with arylboronic acids
  作者：Chunming Zhang、Mark L Trudell

  DOI：10.1016/s0040-4039(99)02133-4

  日期：2000.1

  A series of bisimidazolium salts 1–6 were synthesized and evaluated as precursors to bisimidazol-2-ylidene ligands in palladium-catalyzed Suzuki cross-coupling reactions with aryl chlorides and arylboronic acids. The bisimidazolium salt 6 was found to be superior over imidazolium and other bisimidazolium salts affording high yields of biaryl products employing a wide variety of substrates.

  一系列双咪唑盐的1 - 6合成和评价为前体bisimidazol -2-亚基配体与芳基氯和芳基硼酸的钯-催化的Suzuki交叉偶联反应。发现双咪唑鎓盐6优于咪唑鎓和其他双咪唑鎓盐，它们提供了使用多种底物的高产率的联芳基产物。
• Synthesis of a Novel Chiral Binaphthyl Phospholane and Its Application in the Highly Enantioselective Hydrogenation of Enamides
  作者：Dengming Xiao、Zhaoguo Zhang、Xumu Zhang

  DOI：10.1021/ol991074m

  日期：1999.11.1

  enantiomerically pure binaphthanol. This ligand possesses both binaphthyl chirality and phospholane functionality. Excellent enantioselectivities (95-99.6% ee) have been observed in hydrogenation of an isomeric mixture of (E)- and (Z)-beta-substituted-alpha-arylenamides by using a Rh-binaphane catalyst. These enantioselectivities are the highest reported to date for this transformation.

  [式：见正文]一种新的手性膦，（R，R）-1,2-双[（R）-4,5-二氢-3H-二萘并[2,1- c：1'，2'-e根据实际路线，从容易获得的对映体纯的联萘酚制备[膦]苯] [缩写为（R，R）-联萘芬]。该配体同时具有联萘基手性和膦酰基官能团。在通过使用Rh-联苯甲酰胺催化剂的（E）-和（Z）-β-取代的α-芳基酰胺的异构体混合物的氢化中，观察到了极好的对映选择性（95-99.6％ee）。这些对映选择性是迄今为止报道的最高转化率。
• Magnesium anthracene: an alternative to magnesium in the high yield synthesis of Grignard reagents
  作者：Colin L. Raston、Geoffrey Salem

  DOI：10.1039/c39840001702

  日期：——

  Benzylic type di-Grignard reagents (2)–(5) and the mono-Grignard reagent (6) have been prepared by treating the appropriate organic chloride, for (2)–(6), or bromide, for (3) and (4), with magnesium anthracene in tetrahydroguran in yields of, repectively, 92–96%, and 60 and 84%.

  通过处理（2）–（6）的适当有机氯化物或（3）和（B）的溴化物，制备了Benzylic型双格氏试剂（2）-（5）和单格氏试剂（6）。 4）蒽蒽在四氢古兰糖中的产率分别为92–96％，60和84％。
• Novel Chiral Biaryl Bis(oxazolines)
  作者：Rutger D. Puts、Jade Chao、Dotsevi Y. Sogah

  DOI：10.1055/s-1997-1213

  日期：1997.4

  Novel chiral biaryl bis(oxazoline) have been prepared through a complimentary use of three synthetic methods. The method of choice is determined by the structure of the oxazoline. For bis(oxazolines) containing ethylene spacers between the aromatic ring and the oxazoline groups, a general alkylation procedure based on 2-methyl-2-oxazoline has been developed and found to give very good yields (75-87%) of the desired products. Bis(oxazolines) with the oxazoline moiety attached directly to the aromatic ring were prepared by Ullmann coupling of the appropriate bromoaryl oxazolines. Those containing oxymethylene spacers were prepared by the standard method involving condensation of amino alcohols with the appropriate dicarboxylic acids (84).

  通过互补使用三种合成方法，制备出了新型手性双芳基双（噁唑啉）。选择哪种方法取决于噁唑啉的结构。对于在芳香环和噁唑啉基团之间含有乙烯间隔的双（噁唑啉），已开发出一种基于 2-甲基-2-噁唑啉的通用烷基化程序，并发现该程序可获得非常高产率（75-87%）的所需产物。通过乌尔曼偶联适当的溴芳基噁唑啉，制备出芳香环上直接连接有噁唑啉分子的双噁唑啉。含有氧亚甲基间隔物的双噁唑啉是通过氨基醇与适当的二羧酸缩合的标准方法制备的 (84)。