(R)-3,3'-diformyl-2,2'-dihydroxy-5.5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: (R)-3,3'-diformyl-2,2'-dihydroxy-5.5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl
• 英文别名: (R)-3,3'-diformyl-H8-BINOL；4-(3-Formyl-2-hydroxy-5,6,7,8-tetrahydronaphthalen-1-yl)-3-hydroxy-5,6,7,8-tetrahydronaphthalene-2-carbaldehyde
• 化学式: C₂₂H₂₂O₄
• 分子量: 350.414
• InChiKey: BKSLFPFSKJSHCZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  26
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  74.6
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R)-3,3'-diformyl-2,2'-dihydroxy-5.5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl 在 三乙胺 作用下， 以 甲醇 、 二氯甲烷 、 乙腈 为溶剂， 反应 51.0h， 生成
  参考文献：
  名称：

  不对称催化共聚中的分子内伙伴：在提高温度和低负载下高度对映选择性和可控

  摘要：

  通过分子内双金属和多手性协同催化，在低催化剂负载量或/和提高温度下内消旋环氧化物和酸酐的不对称共聚中实现了优异的对映选择性、活性和无酯交换副反应。

  DOI：

  10.1002/anie.202202585
• 作为产物：
  描述：

  (R)-5,5',6,6',7,7',8,8'-八氢-[1,1'-联萘]-2,2'-二酚 在 正丁基锂 、 四甲基乙二胺 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 生成 (R)-3,3'-diformyl-2,2'-dihydroxy-5.5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl
  参考文献：
  名称：

  Study of the Fluorescent Properties of Partially Hydrogenated 1,1′-Bi-2-naphthol-amine Molecules and Their Use for Enantioselective Fluorescent Recognition

  摘要：

  The fluorescent properties of a series of H8BINOL-amine compounds are investigated. It is revealed that the intramolecular hydrogen bonds of these compounds contribute I to the shift of the emission of their H8BINOL unit to a much longer wavelength. That is, the emission of H8BINOL is at lambda = 323 nm, but that of the H8BINOL-amino alcohol (S)-5 is at lambda = 390 nm. Binding of (3)-5 with mandelic acid suppresses its intramolecular hydrogen bonding and restores the short wavelength emission of the H8BINOL unit. When (S)-s (1.0 x 10(-4) in CH2Cl2) was treated with (R)-mandelic acid (4.0 x 10(-3)), a large fluorescence enhancement at the short wavelength (lambda(emi) = 330 nm) was observed with I-R/I-0 = 11.7. When (S)-MA was used under the same conditions, the enhancement at the short wavelength emission was much smaller. Thus, a good enantioselective fluorescent response was observed with ef =3.5 [ef: enantioselective fluorescence enhancement ratio = (I-R - I-0)/(I-S - I-0)]. This study demonstrates that the H8BINOL-based molecules are promising as a new class of enantioselective fluorescent sensors.

  DOI：

  10.1021/jo200226k

文献信息

• Enantioselective Resolution Copolymerization of <i>Racemic</i> Epoxides and Anhydrides: Efficient Approach for Stereoregular Polyesters and Chiral Epoxides
  作者：Jie Li、Bai-Hao Ren、Zhao-Qian Wan、Shi-Yu Chen、Ye Liu、Wei-Min Ren、Xiao-Bing Lu

  DOI：10.1021/jacs.9b02722

  日期：2019.6.5

  strategy for preparing isotactic polyesters and chiral epoxides via enantioselective resolution copolymerization of racemic terminal epoxides with anhydrides, mediated by enantiopure bimetallic complexes in conjunction with a nucleophilic cocatalyst. The chirality of both the axial linker and the diamine backbones of the ligand are responsible for the chiral induction of this kinetic resolution copolymerization

  在此，我们报告了一种通过外消旋末端环氧化物与酸酐的对映选择性拆分共聚制备全同立构聚酯和手性环氧化物的有效策略，由对映纯双金属配合物与亲核助催化剂共同介导。轴向接头和配体的二胺主链的手性是造成该动力学拆分共聚过程的手性诱导的原因。该催化剂体系表现出非凡的对映选择性水平，对于各种外消旋环氧化物的动力学分辨率超过 300，提供具有完全交替结构和低多分散指数的高度全同立构共聚物（选择性因子超过 300）。
• Facile Synthesis of a Family of H₈BINOL-Amine Compounds and Catalytic Asymmetric Arylzinc Addition to Aldehydes
  作者：Albert M. DeBerardinis、Mark Turlington、Jason Ko、Laura Sole、Lin Pu

  DOI：10.1021/jo1000516

  日期：2010.5.7

  compounds, especially for the challenging ortho-substituted aromatic aldehydes. A H8BINOL-AM with 3,3′-bis-sec-amine substituents, prepared by a multistep method, was also used to catalyze the arylzinc addition to aldehydes, but it showed enantioselectivity lower than that of the compounds with tertiary amine groups. It was found for the first time that an aryl bromide, 2-bromothiophene, could be used

  通过使用H 8 BINOL与氨基甲醇的一步反应，合成了一系列含有3,3'-双叔胺取代基的光学活性H 8 BINOL-AM化合物，氨基甲醇是从各种环状或无环仲胺中原位生成的和多聚甲醛。H 8 BINOL-AM化合物用于催化由芳基碘化物与ZnEt 2的反应原位制备的功能性芳基锌与醛的反应，以生产手性二芳基甲醇和一些芳基烷基甲醇。通过这项研究，确定了高度对映选择性的催化剂。发现H 8具有较不稠密的环状或无环氨基甲基取代基的BINOL-AM化合物比具有较大取代基的BINOL-AM化合物对映选择性更高。在大多数情况下，吡咯烷基衍生物（S）-12表现出比其他H 8 BINOL-AM化合物更高的对映选择性，特别是对于具有挑战性的邻位取代的芳族醛而言。AH 8 BINOL-AM，3,3'-bis- sec通过多步法制得的α-胺取代基也用于催化芳基锌加成醛，但它的对映选择性低于具有叔胺基的化合物。首次发现，可以使用芳基溴化物2-溴噻吩与ZnEt
• 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
• Chiral dinuclear vanadium(v) catalysts for oxidative coupling of 2-naphthols
  作者：Shinobu Takizawa、Tomomi Katayama、Chiaki Kameyama、Kiyotaka Onitsuka、Takeyuki Suzuki、Takeshi Yanagida、Tomoji Kawai、Hiroaki Sasai

  DOI：10.1039/b717068h

  日期：——

  Preparation and structural analysis of chiral dinuclear vanadium(V) catalysts with high catalytic activity for the oxidative coupling of 2-naphthols are described.

  介绍了具有高催化活性的手性双核钒（V）催化剂的制备和结构分析，该催化剂可用于 2-萘酚的氧化偶联。
• Highly Enantioselective Strecker Reaction of Ketoimines Catalyzed by an Organocatalyst from (S)-BINOL andL-Prolinamide
  作者：Zongrui Hou、Jun Wang、Xiaohua Liu、Xiaoming Feng

  DOI：10.1002/chem.200800454

  日期：2008.5.19