(R)-7,7-bis(benzyloxy)-2,2'-dihydroxy-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)-7,7-bis(benzyloxy)-2,2'-dihydroxy-1,1'-binaphthyl
• 英文别名: (R)-(-)-7,7'-bis-benzyloxy-[1,1']-binaphthalene-2,2'-diol；1-(2-hydroxy-7-phenylmethoxynaphthalen-1-yl)-7-phenylmethoxynaphthalen-2-ol
• 化学式: C₃₄H₂₆O₄
• 分子量: 498.578
• InChiKey: ALXSNSITIMQMCC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.3
• 重原子数：
  38
• 可旋转键数：
  7
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R)-7,7-bis(benzyloxy)-2,2'-dihydroxy-1,1'-binaphthyl 生成 2-[37-[2-(diethylamino)ethoxy]-1'-ethyl-17,23,40,43-tetramethylspiro[10,15,25,30-tetraoxaheptacyclo[29.6.2.26,9.216,19.221,24.02,7.034,38]pentatetraconta-1(37),2,4,6,8,16(43),17,19(42),21,23,31(39),32,34(38),35,40,44-hexadecaene-20,4'-piperidine]-3-yl]oxy-N,N-diethylethanamine
  参考文献：
  名称：

  CASTO, PETER P.;GEORGIADIS, TAXIARCHIS M.;DIEDERICH, FRANCOIS, J. ORG. CHEM., 54,(1989) N5, C. 5835-5838

  摘要：

  DOI：
• 作为产物：
  描述：

  3-bromonaphthalene-2,7-diol 在 palladium on activated charcoal 盐酸 、 ammonium formate 、 potassium carbonate 、 叔丁胺 、 copper dichloride 作用下， 以 四氢呋喃 、 甲醇 、 氯仿 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 8.0h， 生成 (R)-7,7-bis(benzyloxy)-2,2'-dihydroxy-1,1'-binaphthyl
  参考文献：
  名称：

  Molecular Recognition of Pyranosides by a Family of Trimeric, 1,1′-Binaphthalene-Derived Cyclophane Receptors

  摘要：

  The synthesis and carbohydrale-recognition properties of a new family of optically active cyclophane receptors, 1-3, in which three 1,1'-binaphthalene-2,2'-diol spacers are interconnected by three bula-1,3-diynediyl linkers, are described. The macrocycles all contain highly preorganized cavities lined with six convergent OH groups for H-bonding and complementary in size and shape to monosaccharides. Compounds 1-3 differ by the functionality attached to the major groove of the 1,1'-binaphthalene-2.2'-diol spacers. The major grooves of the spacers in 2 are unsubstituted, whereas those in 1 bear benzyloxy (BnO) groups in the 7,7'-positions and those in 3 2-phenylethyl groups in the 6,6'-positions. The preparation of the more planar, D-3-symmetrical receptors (R,R,R)-1(Schemes I and 2), (S,S;S)-1 (Scheme 4), (S,S,S)-2 (Scheme 5), and (S,S,S)-3 (Scheme 8) involved as key step the Glaser-Hay cyclotrimerization of the corresponding OH-protected 3,3'-dielhynyl-1,1'-binaphthalene-2,2'-diol precursors, which yielded tetrameric and pentameric macrocycles in addition to the desired trimeric compounds. The synthesis of the less planar, C-2-symmetrical receptors (R,R,S)-2 (Scheme 6) and (S,S,R)-3 (Scheme 9) proceeded via two Glaser-Hay coupling steps. First, two monomeric precursors of identical configuration were oxidatively coupled to give a dimeric intermediate which was then subjected to macrocyclization with a third monomeric 1,1'-binaphthalene precursor of opposite configuration. The 3,3'-dialkynylation of the OH-protected 1,1'-binaphthalene-2,2'-diol precursors for the macrocyclizations was either performed by Stifle (Scheme I) or by Sonogashira (Schemes 4, 5, and 8) cross-coupling reactions. The flat D-3-symmetrical receptors (R,R,R)-1 and (S,S,S)-1 formed 1:1 cavity inclusion complexes with octyl 1-O-pyranosides in CDCl3 (300 K) with moderate stability (Delta G degrees ca. -3 kcal mol(-1)) as well as moderate diastereo(Delta(Delta G degrees) up to 0.7 kcal mol(-1)) and enantioselectivity (Delta(Delta G degrees) = 0.4 kcal mol(-1)) ( Table I). Stoichiometric 1 : 1 complexation by (S,S,S)-2 and (S,S,S)3 could not be investigated by H-1-NMR binding titrations, due to very strong signal broadening. This broadening of the H-1-NMR resonances is presumably indicative of higher-order associations, in which the planar macrocycles sandwich the carbohydrate guests. The less planar Ct-symmetrical receptor (S,S,R)-3 formed stable 1: 1 complexes with binding free enthalpies of up to Delta G degrees = - 5.0 kcal mol(-1) (Table 2). With diastereoselectivities up to Delta(Delta G degrees)=1.3 kcal mol(-1) and enantioselectivities of Delta(Delta G degrees)= 0.9 kcal mol(-1), (S,S,R)-3 is among the most selective artificial carbohydrate receptors known.

  DOI：

  10.1002/(sici)1522-2675(19981111)81:11<1931::aid-hlca1931>3.0.co;2-5
• 作为试剂：
  描述：

  烯丙基三丁基锡 、 苯甲醛 在 二异丙氧基二氯化钛 (R)-7,7-bis(benzyloxy)-2,2'-dihydroxy-1,1'-binaphthyl 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 1.5h， 生成 (S)-1-苯基-3-丁烯-1-醇 、 (R)-1-Phenylbut-3-en-1-ol
  参考文献：
  名称：

  Bandin, Marco; Casolari, Sonia; Cozzi, Pier Giorgio, European Journal of Organic Chemistry, 2000, # 3, p. 491 - 497

  摘要：

  DOI：

文献信息

• Enantioselective Iron/Bisquinolyldiamine Ligand-Catalyzed Oxidative Coupling Reaction of 2-Naphthols
  作者：Lin-Yang Wu、Muhammad Usman、Wen-Bo Liu

  DOI：10.3390/molecules25040852

  日期：——

  An iron-catalyzed asymmetric oxidative homo-coupling of 2-naphthols for the synthesis of 1,1′-Bi-2-naphthol (BINOL) derivatives is reported. The coupling reaction provides enantioenriched BINOLs in good yields (up to 99%) and moderate enantioselectivities (up to 81:19 er) using an iron-complex generated in situ from Fe(ClO4)2 and a bisquinolyldiamine ligand [(1R,2R)-N1,N2-di(quinolin-8-yl)cyclohexane-1

  报道了用于合成 1,1'-Bi-2-萘酚 (BINOL) 衍生物的铁催化的 2-萘酚的不对称氧化均偶联。偶联反应使用由 Fe(ClO4)2 和双喹啉二胺配体 [(1R,2R) -N1,N2-二(喹啉-8-基)环己烷-1,2-二胺，L1]。在氧化偶联反应中合成并检查了许多配体（L2-L8）和 L1 的类似物，具有各种取代基和手性骨架。
• Chiral catalyst, process for preparing the same and its use in the oxidate coupling of naphthols
  申请人：Gong Liuzhu

  公开号：US20050256345A1

  公开（公告）日：2005-11-17

  The compound of this invention is a useful catalyst for the oxidative coupling of naphthol. Its originality lies in that it is a novel vanadium complex of Schiff's base formed by a chiral amino acid and a formyl biphenol or its derivative. Its axis chirality is induced to form by the chiral amino acid. It has the general formula: where R represents a benzyl, an isopropyl, an isobutyl or a tertiary butyl and the configuration of the amino acid is R or S. The compound can catalyze oxidative coupling of naphthol or its derivative to form binaphthol or its derivatives with a high optical purity.

  这项发明的化合物是一种用于萘酚氧化偶联的有用催化剂。其独特之处在于它是一种新颖的茜素碱的钒络合物，由手性氨基酸和甲酰联苯酚或其衍生物形成。其轴手性是由手性氨基酸诱导形成的。它的一般化学式为：其中R代表苄基、异丙基、异丁基或叔丁基，氨基酸的构型是R或S。该化合物可以催化萘酚或其衍生物的氧化偶联反应，形成具有高光学纯度的联萘酚或其衍生物。
• Enantioselective Oxidative Homocoupling and Cross-Coupling of 2-Naphthols Catalyzed by Chiral Iron Phosphate Complexes
  作者：Sachin Narute、Regev Parnes、F. Dean Toste、Doron Pappo

  DOI：10.1021/jacs.6b11198

  日期：2016.12.21

  Novel chiral iron phosphate complexes were prepared as catalysts for asymmetric oxidative coupling reactions. These catalysts were applied for the synthesis of enantio-enriched C1- and C2-symmetric BINOLs, in which the 3 and 3' positions are available for chemical modifications. It was proposed that the reaction takes place via an oxidative radical-anion coupling mechanism. A destructive BINOL racemization

  制备了新型手性磷酸铁配合物作为不对称氧化偶联反应的催化剂。这些催化剂用于合成富含对映体的 C1 和 C2 对称 BINOL，其中 3 和 3' 位置可用于化学修饰。有人提出该反应是通过氧化自由基 - 阴离子偶联机制发生的。揭示了与 2-萘酚的对映选择性氧化偶联竞争的破坏性 BINOL 外消旋化，从而为这一非常重要的反应提供了新的见解。
• Highly Enantioselective Oxidative Couplings of 2-Naphthols Catalyzed by Chiral Bimetallic Oxovanadium Complexes with Either Oxygen or Air as Oxidant
  作者：Qi-Xiang Guo、Zhi-Jun Wu、Zhi-Bin Luo、Quan-Zhong Liu、Jian-Liang Ye、Shi-Wei Luo、Lin-Feng Cun、Liu-Zhu Gong

  DOI：10.1021/ja074322f

  日期：2007.11.1

  L-isoleucine and H8-binaphthol is highly efficient at catalyzing the air-oxidized coupling of 2-naphthols with excellent enantioselectivities of up to 97% ee. 51V NMR study shows that the oxovanadium complexes have two vanadium(V) species. Kinetic studies, the cross-coupling reaction, and HRMS spectral studies on the reaction have been carried out and illustrate that two vanadium(V) species are both involved

  手性双金属氧钒配合物已被设计用于在 C6 和/或 C7 处带有各种取代基的 2-萘酚的对映选择性氧化偶联。使用 UV 和 CD 光谱以及 DFT 计算发现，在氧钒配合物 2 中，手性从氨基酸转移到联苯的轴上。以氧为氧化剂的均偶联反应由 5 mol% 的 L-异亮氨酸和非手性双酚衍生的氧钒配合物促进，以接近定量的产率提供联萘酚，对映选择性高达 98% ee。源自 L-异亮氨酸和 H8-联萘酚的氧钒配合物可高效催化 2-萘酚的空气氧化偶联，具有高达 97% ee 的出色对映选择性。51V NMR 研究表明氧钒配合物具有两种钒 (V) 物质。对该反应进行了动力学研究、交叉偶联反应和 HRMS 光谱研究，表明两种钒 (V) 物种都参与催化，并且偶联反应以分子内方式经历自由基 - 自由基机制。量子力学计算合理化了轴向手性匹配 S-氨基酸对氧化偶联反应立体控制的协同作用的重要性。转化在制备手性配体和共
• Linker-Oriented Design of Binaphthol Derivatives for Optical Resolution Using Lipase-Catalyzed Reaction
  作者：Tomohiro Taniguchi、Taka-aki Fukuba、Shuhei Nakatsuka、Shuichi Hayase、Motoi Kawatsura、Hidemitsu Uno、Toshiyuki Itoh

  DOI：10.1021/jo800351h

  日期：2008.5.1

  ethoxynaphthalen-1-yl)-6-bromonaphthalen-2-yloxy)butanoate was hydrolyzed by CAL-B to afford a corresponding acid with excellent enantioselectivity (E > 200). Two types of optically active binaphthol derivatives, 1-(2-hydroxy-6-(naphthalen-1-yl)naphthalen-1-yl)-6-(naphthalen-1-yl)naphthalen-2-ol and 6-butyl-1-(6-butyl-2-hydroxynaphthalen-1-yl)naphthalen-2-ol, were prepared by this chemo-enzymatic reaction

  南极假丝酵母脂肪酶B（CAL-B）是有机合成中最常用的酶，用于制备旋光性醇。但是，尚未用于（±）-2,2'-联萘酚的光学拆分。我们建立了一种有效的针对2,2'-联萘酚衍生物的面向接头的设计，该设计适合使用CAL-B催化的水解反应进行光学拆分。用CAL-B水解4-（1-（6-溴-2-甲氧基甲氧基萘-1-基）-6-溴萘-2-基氧基）丁酸甲酯，得到具有优异对映选择性的相应酸（E> 200）。两种类型的光学活性联萘酚衍生物，1-（2-羟基-6-（萘-1-基）萘-1-基）-6-（萘-1-基）萘-2-醇和6-丁基-通过该化学酶促反应方案制备1-（6-丁基-2-羟基萘-1-基）萘-2-醇，并用作对称反应的手性模板。