Tetrahydro-β-dinaphthol

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: Tetrahydro-β-dinaphthol
• 英文别名: 1-(2-hydroxy-5,6,7,8-tetrahydronaphthalen-1-yl)naphthalen-2-ol
• 化学式: C₂₀H₁₈O₂
• 分子量: 290.362
• InChiKey: RIIPKVKLCGYGAE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  22
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  Tetrahydro-β-dinaphthol 在 溴 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以91%的产率得到6-Bromo-1-(3-bromo-2-hydroxy-5,6,7,8-tetrahydronaphthalen-1-yl)naphthalen-2-ol
  参考文献：
  名称：

  3,3'-茴香基取代的BINOL，H 4 BINOL和H 8 BINOL配体：多元炔丙基醇的不对称合成及其手性环烯烃的环封闭复分解

  摘要：

  制备了一系列光学活性的BINOL，H 4 BINOL和H 8 BINOL衍生物。这些化合物与ZnEt 2和Ti（O i Pr）4结合用于在室温下催化炔烃与醛的不对称反应以生成手性炔丙醇。通过比较研究，发现3,3'-双茴香基取代的H 8 BINOL（S）-7已发现其是通常的对映选择性催化剂，其用于结构多样的末端炔烃与各种醛的反应。它催化了ee值为88-99％的丙酸烷基酯的反应。苯乙炔与ee为81-87％的反应; 4-苯基-1-丁炔，一种烷基炔，与77-89％ee的反应；和三甲基甲硅烷基乙炔与92-97％ee的反应。观察到由这种催化不对称炔烃加成产生的旋光性炔丙醇在Grubbs II催化剂的存在下进行了有效的闭环复分解（RCM）反应，生成了手性环烯烃。进一步发现，一些手性炔丙基醇进行了高度化学选择性的串联RCM氢化反应，同时保留了对映体纯度。

  DOI：

  10.1021/jo9018446
• 作为产物：
  描述：

  (S)-2-(2,2-dimethylbutyryl)oxy-2'-hydroxy-5',6',7',8'-tetrahydro-1,1'-binaphthyl 在 sodium hydroxide 、 水 作用下， 反应 12.0h， 以100%的产率得到Tetrahydro-β-dinaphthol
  参考文献：
  名称：

  A Convenient Synthesis of (S)-H₄-BINOL and Its Derivatives via Hydrogenation of Monoesters of BINOL

  摘要：

  A new multigram synthesis of chiral (S)-H-4-BINOL and its derivatives in moderate to high yield (up to 83% total yield) via monoesterification of (S)-BINOL, hydrogenation, and saponification reaction was described. The two new monomethylated (S)-H-4-BINOL obtained may be useful materials in asymmetric catalysis.

  DOI：

  10.1021/jo802542m
• 作为试剂：
  描述：

  反式肉桂醛 、 反-1-甲氧基-3-(三甲基硅氧基)-1,3-丁二烯 在 Tetrahydro-β-dinaphthol titanium(IV) isopropylate 作用下， 反应 96.0h， 以82%的产率得到(R)-2-(E)-styryl-2,3-dihydro-4H-pyran-4-one
  参考文献：
  名称：

  Discovery of Exceptionally Efficient Catalysts for Solvent-Free Enantioselective Hetero-Diels−Alder Reaction

  摘要：

  Combinatorial coordination chemistry strategy combined with high-throughput screening techniques has been successfully applied to engineering practical enantioselective catalysts for asymmetric hetero-Diels-Alder reaction. The reaction of Danishefsky's diene with a variety of aldehydes can be carried out with 0.1-0.005 mol % of H4-BINOL/Ti/H4-BINOL or H4-BINOL/Ti/H8-BINOL catalysts at room temperature under solvent- and MS-free conditions to afford dihydropyrone derivatives with up to quantitative yield and 99.8% ee.

  DOI：

  10.1021/ja0172518

文献信息

• METHOD FOR MANUFACTURING OPTICALLY ACTIVE MENTHOL
  申请人：Tsuda Toshiro

  公开号：US20130253228A1

  公开（公告）日：2013-09-26

  An object of the present invention is to provide a method for manufacturing an optically active menthol having fewer steps, which generates less environmentally polluting waste because a catalytic reaction is involved in all of the steps, and is capable of saving a production cost. The present invention relates to a method for manufacturing an optically active menthol, including the following steps: A-1) asymmetrically hydrogenating at least one of geranial and neral to thereby obtain an optically active citronellal, B-1) conducting a ring-closure reaction of the optically active citronellal in the presence of an acid catalyst to thereby obtain an optically active isopulegol, and C-1) hydrogenating the optically active isopulegol to thereby obtain an optically active menthol.

  本发明的目的是提供一种制造具有较少步骤的光学活性薄荷醇的方法，因为所有步骤都涉及催化反应，所以产生的环境污染废物较少，并且能够节省生产成本。本发明涉及一种制造光学活性薄荷醇的方法，包括以下步骤：A-1）不对称地氢化至少一种香叶醛和柠檬醛以获得光学活性柠檬醛，B-1）在酸催化剂存在下对光学活性柠檬醛进行环闭合反应，从而获得光学活性异薄荷醇，以及C-1）对光学活性异薄荷醇进行氢化以获得光学活性薄荷醇。
• [EN] ALUMINIUM COMPLEXES AND USE THEREOF AS A CATALYST IN INTRAMOLECULAR RING CLOSURE REACTIONS<br/>[FR] COMPLEXES D'ALUMINIUM ET LEUR UTILISATION EN TANT QUE CATALYSEUR DANS DES RÉACTIONS INTRAMOLÉCULAIRES DE FERMETURE DE CYCLE
  申请人：TAKASAGO PERFUMERY CO LTD

  公开号：WO2010071227A1

  公开（公告）日：2010-06-24

  To provide a process for increasing the proportion of an optical isomer of not only a compound having a closed ring but also a compound not having a closed ring when an optical isomer mixture of a compound having both a formyl group and a double bond capable of causing a carbonyl-ene ring closing reaction in the same molecule is subjected to a ring closing reaction. A process for increasing the proportion of an optical isomer characterized by subjecting an optical isomer mixture of a compound having both a formyl group and a double bond capable of causing a carbonyl-ene ring closing reaction in the same molecule to a ring closing reaction in the presence of a predetermined aluminum complex represented by the general formula: [Al2(L1)n(L2)3-n]m.

  提供一种增加光学异构体比例的过程，不仅适用于具有闭环的化合物，也适用于不具有闭环的化合物，当具有甲醛基和能够在同一分子中引起羰基-烯烃环闭合反应的双键的化合物的光学异构体混合物经过环闭合反应时。一种增加光学异构体比例的过程，其特征在于将具有甲醛基和能够在同一分子中引起羰基-烯烃环闭合反应的双键的化合物的光学异构体混合物在预定的铝配合物存在下进行环闭合反应，该铝配合物由通式表示：[Al2(L1)n(L2)3-n]m。
• ORGANOALUMINUM COMPOUND
  申请人：ITOH Hisanori

  公开号：US20110295031A1

  公开（公告）日：2011-12-01

  A catalyst for obtaining isopulegol of high diastereoselectivity by highly selective cyclization reaction of citronellal is provided. The present invention relates to an organoaluminum compound obtained by reacting at least one organoaluminumoxy compound selected from the group consisting of chain aluminoxanes, cyclic aluminoxanes and bis(dialkylaluminumoxy)alkylboranes, with at least one hydroxy compound selected from the group consisting of diarylphenols, bis(diarylphenol) compounds, biaryldiols, dimethanols and silanols.

  本发明提供了一种催化剂，用于通过高度选择性的环化反应从香茅醛中获得高对映选择性的异莰醇。本发明涉及通过将链状铝氧烷、环状铝氧烷和双(二烷基氧基)烷基硼烷等组中至少一种有机铝氧化合物与二苯基酚、双(二苯基酚)化合物、联苯二醇、二甲醇和硅烷等组中至少一种羟基化合物反应而得到的有机铝化合物。
• ALUMINUM COMPLEX AND USE THEREOF
  申请人：Itoh Hisanori

  公开号：US20110082308A1

  公开（公告）日：2011-04-07

  Provided is a process in which cyclization of a compound having, in a molecule, a formyl group and a double bond which allow carbonyl-ene cyclization, the compound existing as a mixture of optical isomers thereof, increases the ratio of a particular optical isomer not only in a cyclized compound, but also in an unreacted compound. The process comprises performing, in the presence of a specified aluminum complex represented by the general formula: [Al 2 (L 1 ) n (L 2 ) 3-m ] m , cyclization of a compound having, in a molecule, a formyl group and a double bond which allow carbonyl-ene cyclization, the compound existing as a mixture of optical isomers thereof, to increase the ratio of a particular optical isomer.

  提供的是一种过程，在分子中具有甲酰基和双键的化合物进行环化反应，从而允许羰基-烯环化反应，该化合物存在其光学异构体的混合物中，不仅可以增加环化后化合物中特定光学异构体的比例，还可以增加未反应化合物中特定光学异构体的比例。该过程包括在指定的铝配合物存在下进行环化反应，该铝配合物由通式[Al2(L1)n(L2)3-m]m表示，化合物在分子中具有甲酰基和双键，允许羰基-烯环化反应，化合物存在其光学异构体的混合物中，以增加特定光学异构体的比例。
• Synthesis of modified H4-BINOL ligands and their applications in the asymmetric addition of diethylzinc to aromatic aldehydes
  作者：Yong-Na Lu、Qun-Sheng Guo、Fu-Yong Jiang、Jin-Shan Li

  DOI：10.1016/j.tetasy.2006.06.042

  日期：2006.7

  Two new ligands (S,S)-3-(1,1'-bi-2-naphthol-3-yl)-5,6,7,8-tetrahydro-1,1'-bi-2-naphthol [(S,S)-1] and (S)-3-(morpholin-4-yl-methyl)-H-4-BINOL [(S)-2] have been synthesized via Suzuki cross-coupling reaction and a Mannich-type reaction, respectively. In the presence of titanium tetraisopropoxide, 0.8 mol% of ligand (S,S)-1 catalyzed the asymmetric addition of diethylzinc to aromatic aldehydes in good yield and with high enantioselectivity. (c) 2006 Elsevier Ltd. All rights reserved.