(S)-2,2′-dihydroxy-1,1′-binaphthyl-3-carboxylic acid

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (S)-2,2′-dihydroxy-1,1′-binaphthyl-3-carboxylic acid
• 英文别名: (S)-3-hydroxy-4-(2-hydroxynaphthalene-1-yl)-2-naphthoic acid；(S)-3-hydroxy-4-(2-hydroxynaphthalen-1-yl)-2-naphthoic acid；(S)-2,2'-Dihydroxy-[1,1'-binaphthalene]-3-carboxylic acid；(S)-1,1'-binaphthyl-2,2'-dihydroxy-3-carboxylic acid；(S)-2,2'-dihydroxy-1,1'-binaphthyl-3-carboxylic acid；1,1'-binaphthyl-2,2'-dihydroxy-3-carboxylic acid；2,2'-Dihydroxy-3-carboxy-1,1'-binaphthyl；3-hydroxy-4-(2-hydroxynaphthalen-1-yl)naphthalene-2-carboxylic acid
• 化学式: C₂₁H₁₄O₄
• 分子量: 330.34
• InChiKey: VMUYFZVUURXESF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  25
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  77.8
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (S)-2,2′-dihydroxy-1,1′-binaphthyl-3-carboxylic acid 在 sodium hydroxide 作用下， 以 甲醇 、 水 为溶剂， 反应 20.0h， 生成
  参考文献：
  名称：

  Asymmetric Phase-Transfer Catalysis by Quaternary Ammonium Ions Derived fromCinchona-Alkaloid Analogs Containing 1,1′-Binaphthalene Moieties

  摘要：

  The synthesis and catalytic properties of a new type of enantioselective phase-transfer catalysts, incorporating both the quinuclidinemethanol fragment of Cinchona alkaloids and a 1,1'-binaphthalene moiety, are described. Catalyst (+)-(aS,3R,4S,8R,9S)-4 with the quinuclidine fragment attached to C(7') in the major groove of the 1,1'-binaphthalene residue was predicted by computer modeling to be an efficient enantioselective catalyst for the unsymmetric alkylation of 6,7-dichloro-5-methoxy-2-phenylindanone (1; Scheme I, Fig. I). Its synthesis involved the selective oxidative cross-coupling of two differently substituted naphthalen-2-ols to afford the asymmetrically substituted 1,1'-binaphthalene derivative (+/-)-17 in high yield (Scheme 3). Chromatographic optical resolution via formation of diastereoisomeric camphorsulfonyl esters and functional-group manipulation gave access to the 7-bromo-1,1'-binaphthalene derivative (-)-(aS)-11 (Scheme 4). Nucleophilic addition of lithiated (-)-(aS)-11 to the quinuclidine Weinreb amide (+)-(3R,4S,8R)-8 afforded the two ketones (aS,3R,4S,8R)-27 and (aS,3R,4S,8S)-28 as an inseparable mixture of diastereoisomers (Scheme 6). Stereoselective reduction of this mixture with DIBAL-H (diisobutylaluminum hydride; preferred formation of the C(8)-C(9) erythro-pair of diastereoisomers with 18% de) or with NaBH4 (preferred formation of the threo-pair of diastereoisomers with 50% de) afforded the four separable diastereoisomers (+)-(aS,3R,4S,8S,9S)-29, (+)-(aS,3R,4S,8R,9R)-30, (-)-(aS,3R,4S,8S,9R)-31, and (+)-(aS,3R,4S,8R,9S)-32 (Scheme 6). A detailed conformational analysis, combining H-1-NMR spectroscopy and molecular-mechanics computations, revealed that the four diastereoisomers displayed distinctly different conformational preferences (Figs. 2 and 3). These novel Cinchona-alkaloid analogs were quaternized to give (+)-(aS,3R,4S,8R,9S)-4, (+)-(aS,3R,4S,8S,9S)-5, (+)(aS,3R,4S,8R,9R)-6, and (-)-(aS,3R,4S,8S,9R)-7 (Scheme 7) which were tested as phase-transfer agents in the asymmetric allylation of phenylindanone 1. Without any optimization work, (+)-(aS,3R,4S,8R,9S)-4 was found to catalyze the allylation of 1 yielding the predicted enantiomer (+)-(S)-3b in 32% ee. The three diastereoisomeric catalysts (+)-5, (+)-6, and (-)-7 gave access to lower enantioselectivities (6 to 22% ee's), which could be rationalized by computer modeling (Fig. 4).

  DOI：

  10.1002/(sici)1522-2675(19990707)82:7<981::aid-hlca981>3.0.co;2-v
• 作为产物：
  描述：

  在 sodium hydroxide 作用下， 以 甲醇 、 水 为溶剂， 反应 12.0h， 生成 (S)-2,2′-dihydroxy-1,1′-binaphthyl-3-carboxylic acid
  参考文献：
  名称：

  Asymmetric Phase-Transfer Catalysis by Quaternary Ammonium Ions Derived fromCinchona-Alkaloid Analogs Containing 1,1′-Binaphthalene Moieties

  摘要：

  The synthesis and catalytic properties of a new type of enantioselective phase-transfer catalysts, incorporating both the quinuclidinemethanol fragment of Cinchona alkaloids and a 1,1'-binaphthalene moiety, are described. Catalyst (+)-(aS,3R,4S,8R,9S)-4 with the quinuclidine fragment attached to C(7') in the major groove of the 1,1'-binaphthalene residue was predicted by computer modeling to be an efficient enantioselective catalyst for the unsymmetric alkylation of 6,7-dichloro-5-methoxy-2-phenylindanone (1; Scheme I, Fig. I). Its synthesis involved the selective oxidative cross-coupling of two differently substituted naphthalen-2-ols to afford the asymmetrically substituted 1,1'-binaphthalene derivative (+/-)-17 in high yield (Scheme 3). Chromatographic optical resolution via formation of diastereoisomeric camphorsulfonyl esters and functional-group manipulation gave access to the 7-bromo-1,1'-binaphthalene derivative (-)-(aS)-11 (Scheme 4). Nucleophilic addition of lithiated (-)-(aS)-11 to the quinuclidine Weinreb amide (+)-(3R,4S,8R)-8 afforded the two ketones (aS,3R,4S,8R)-27 and (aS,3R,4S,8S)-28 as an inseparable mixture of diastereoisomers (Scheme 6). Stereoselective reduction of this mixture with DIBAL-H (diisobutylaluminum hydride; preferred formation of the C(8)-C(9) erythro-pair of diastereoisomers with 18% de) or with NaBH4 (preferred formation of the threo-pair of diastereoisomers with 50% de) afforded the four separable diastereoisomers (+)-(aS,3R,4S,8S,9S)-29, (+)-(aS,3R,4S,8R,9R)-30, (-)-(aS,3R,4S,8S,9R)-31, and (+)-(aS,3R,4S,8R,9S)-32 (Scheme 6). A detailed conformational analysis, combining H-1-NMR spectroscopy and molecular-mechanics computations, revealed that the four diastereoisomers displayed distinctly different conformational preferences (Figs. 2 and 3). These novel Cinchona-alkaloid analogs were quaternized to give (+)-(aS,3R,4S,8R,9S)-4, (+)-(aS,3R,4S,8S,9S)-5, (+)(aS,3R,4S,8R,9R)-6, and (-)-(aS,3R,4S,8S,9R)-7 (Scheme 7) which were tested as phase-transfer agents in the asymmetric allylation of phenylindanone 1. Without any optimization work, (+)-(aS,3R,4S,8R,9S)-4 was found to catalyze the allylation of 1 yielding the predicted enantiomer (+)-(S)-3b in 32% ee. The three diastereoisomeric catalysts (+)-5, (+)-6, and (-)-7 gave access to lower enantioselectivities (6 to 22% ee's), which could be rationalized by computer modeling (Fig. 4).

  DOI：

  10.1002/(sici)1522-2675(19990707)82:7<981::aid-hlca981>3.0.co;2-v

文献信息

• Dual Organocatalysis: Asymmetric Allylic-Allylic Alkylation of α,α-Dicyanoalkenes and Morita-Baylis-Hillman Carbonates
  作者：Hai-Lei Cui、Jing Peng、Xin Feng、Wei Du、Kun Jiang、Ying-Chun Chen

  DOI：10.1002/chem.200802534

  日期：2009.2.2

  The first highly enantioselective allylic–allylic alkylation of α,α‐dicyanoalkenes and Morita–Baylis–Hillman carbonates by dual catalysis of (DHQD)2AQN and (S)‐BINOL has been investigated. Excellent stereoselectivities have been achieved for a broad spectrum of substrates (d.r. > 99:1, up to 99 % ee). The multifunctional allylic products could be efficiently converted to a range of complex chiral cyclic

  通过（DHQD）2 AQN和（S）-BINOL的双重催化作用，首次研究了α，α-二氰基烯烃和Morita-Baylis-Hillman碳酸盐的高对映选择性烯丙基-烯丙基烷基化反应。对于广泛的底物（dr> 99：1，高达99％ee），已经实现了出色的立体选择性 。多功能烯丙基产物可以有效地转化为一系列复杂的手性环状骨架。EWG =吸电子基团（DHQD）2 AQN =对苯二酚（蒽醌-1,4-二甲苯基）二醚，（S）-BINOL =（S）-（-）-1,1'-bi-2-萘酚。
• Highly Enantioselective Extraction of Underivatized Amino Acids by the Uryl-Pendant Hydroxyphenyl-Binol Ketone
  作者：Haofei Huang、Qian Chen、Misun Choi、Raju Nandhakumar、Zhishan Su、Sihyun Ham、Kwan Mook Kim

  DOI：10.1002/chem.201304454

  日期：2014.3.3

  extractant. Calculations for the energy‐minimized structures for the imine diastereomers and the comparison of the selectivities with other phenyl ketones, (S)‐4 and (S)‐5, demonstrate that the hydrogen bond between the carboxylate group and the phenolic hydroxyl group contributes to the remarkable enantioselectivities. The multiple hydrogen bonds present in the imine of (S)‐3 reinforce the rigidity

  羟苯基手性酮（S）-3在两相液-液萃取中与L-氨基酸上带有疏水侧链的D-氨基酸反应，因此可以作为高度立体选择性的萃取剂。亚胺非对映异构体能量最小化结构的计算以及与其他苯基酮（S）-4和（S）-5的选择性比较表明，羧酸根和酚羟基之间的氢键有助于出色的对映选择性。（S）-3亚胺中存在多个氢键增强刚性，并导致亚胺非对映异构体的稳定性之间的差异。亚胺可以在HCl甲醇溶液中水解，蒸发残留物的提取使（S）-3的有机层复活，这可能进入一个新的萃取循环，并使D-氨基酸具有对映体过量（ee）值在水层中超过97％。
• Asymmetric [3+2] Cycloaddition of Olefins with Morita–Baylis–Hillman Carbonates Catalyzed by BINOL-Based Bifunctional Phosphine
  作者：Hai-Lei Cui、Xue Tang、Meng-Fan Li、Xing-Jie Xu、Yin Shi

  DOI：10.1055/s-0037-1611752

  日期：2019.4

  series of novel BINOL-based phosphines. These bifunctional organocatalysts can be used in the [3+2] cycloaddition of electron-deficient olefins and Morita–Baylis–Hillman (MBH) carbonates. Moderate to excellent yields (up to >99%) and good to excellent enantioselectivities (up to 95% ee) can be obtained in the cycloaddition reaction of maleimides and MBH carbonates. The application of these novel phosphines

  我们开发了一系列新型的基于 BINOL 的膦。这些双功能有机催化剂可用于缺电子烯烃和 Morita-Baylis-Hillman (MBH) 碳酸酯的 [3+2] 环加成。在马来酰亚胺和 MBH 碳酸酯的环加成反应中可以获得中等至优异的产率（高达 >99%）和良好至优异的对映选择性（高达 95% ee）。这些新型膦的应用可以进一步扩展到手性螺环吲哚的不对称合成（高达 85% ee）。本研究的结果表明 BINOL 部分在立体控制中起着重要作用。
• t-부틸케톤 바이나프톨 유도체 및 이의 제조 방법
  申请人：AMINOLOGICS Co., Ltd. 주식회사 아미노로직스(119987027810) Corp. No ▼ 131111-0030369BRN ▼129-81-23337

  公开号：KR101558949B1

  公开（公告）日：2015-10-08

  본원은 수용액 상의 아미노산을 매우 높은 키랄선택성으로 유기층으로서 추출하고 용이하게 가수분해할 수 있으며 상기 유기층을 계속 재사용할 수 있는 고효율 키랄추출제로서의 t-부틸케톤 바이나프톨 유도체, 및 이의 제조 방법에 관한 것이다.

  该专利涉及一种 t-丁基酮联萘二醇衍生物，作为一种高效的手性萃取剂，具有非常高的手性选择性，可以从溶液中提取氨基酸，并且容易水解，可以持续回收和再利用该有机层，涉及其制备方法。
• Efficient Synthesis of Chiral Binaphthol Aldehyde with Phenyl Ether Linkage for Enantioselective Extraction of Amino Acids
  作者：Misun Choi、Moo-Jin Jun、Kwan Mook Kim

  DOI：10.1002/bkcs.10354

  日期：2015.7

  starting from binaphthol‐3‐carboxylic acid. The axially chiral binaphthol ring was racemized during the synthesis due to high temperatures required in O‐phenylation reaction. The enantiomerically pure form of 2 was obtained from the resolution of the diastereomeric imine of 2. Optically pure compound (S)‐2 was applied to the enantioselective liquid–liquid extraction of amino acid between CH2Cl2 and aqueous

  具有联苯醚键的联萘酚醛化合物2是从联萘酚-3-羧酸开始合成的。由于O-苯基化反应需要高温，因此在合成过程中轴向手性联萘酚环已消旋。的对映体纯形式2从非对映体亚胺的分辨率，得到2。将光学纯的化合物（S）-2应用于CH 2 Cl 2与水层之间氨基酸的对映选择性液-液萃取。立体选择性，即d / l提取的氨基酸的比例为3.57至11.1。一个碳是在化合物（缺席小号- ）2相比，化合物（小号） - 1与苄基醚键，其与微分氨基酸形成其亚胺的构象。