1-(4',6'-dimethoxy-2'-hydroxyphenyl)naphthalene-2-carbaldehyde | 142503-17-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 1-(4',6'-dimethoxy-2'-hydroxyphenyl)naphthalene-2-carbaldehyde
• 英文别名: 'OMe-aldehyde' (TH 3)；1-(2-hydroxy-4,6-dimethoxyphenyl)naphthalene-2-carbaldehyde
• CAS: 142503-17-1
• 化学式: C₁₉H₁₆O₄
• 分子量: 308.334
• InChiKey: BFXXQLDFQRKMAJ-UHFFFAOYSA-N

物化性质

• 沸点：
  483.1±45.0 °C(Predicted)
• 密度：
  1.248±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-(4',6'-dimethoxy-2'-hydroxyphenyl)naphthalene-2-carbaldehyde 在 (S)-2-甲基-CBS-恶唑硼烷 、 儿萘酚硼烷 作用下， 以 甲苯 为溶剂， 反应 1.0h， 生成 (rac)-2-hydroxymethyl-(2',4'-dimethoxy-6'-hydroxyphenyl)-naphthalene
  参考文献：
  名称：

  The Atropo-Enantioselective Reduction of Configurationally Unstable Biaryl Hydroxy Aldehydes - A Novel Approach to Axially Chiral Biaryls

  摘要：

  在噁唑硼烷辅助下，通过（动态）动力学解析将构型不稳定的双芳基羟基醛还原成轴向手性双芳基醇的邻苯二酚硼烷对映体选择性还原，对映体比（er）可达 92:8。使用相同的手性助剂，只需改变非手性还原剂的相对数量，就能以较好的对映体比（er's）获得 M-或 P-配置的异构体。这表明存在着两种具有相反不对称诱导作用的竞争反应途径。观察到的对映体比率在很大程度上取决于双芳基轴正向取代基的相对立体需求。

  DOI：

  10.1055/s-1998-1728
• 作为产物：
  描述：

  2-萘甲醛,1-溴-3,4-二氢- 在 manganese(IV) oxide 、 sodium chlorite 、 sodium dihydrogenphosphate 、 lithium aluminium tetrahydride 、 2-甲基-2-丁烯 、 草酰氯 、 sodium acetate 、 palladium diacetate 、 N,N-二甲基甲酰胺 、 三苯基膦 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基乙酰胺 、 水 、 甲苯 、 叔丁醇 为溶剂， 反应 50.0h， 生成 1-(4',6'-dimethoxy-2'-hydroxyphenyl)naphthalene-2-carbaldehyde
  参考文献：
  名称：

  钌催化还原胺化和动态动力学拆分轴向联芳基的对苯二酚选择性合成

  摘要：

  描述了通过级联转移氢化和动态动力学拆分策略，空前的钌催化的烷基胺对醛的对苯二酸选择性还原胺化反应。该方案具有广泛的底物范围和良好的官能团耐受性，并允许以高至高收率和高至优异的对映选择性快速组装轴向手性联芳基。另外，这样的结构基序可以作为手性配体或催化剂在对映选择性催化中具有潜在的应用。

  DOI：

  10.1021/acs.orglett.8b02785

文献信息

• The Atropo-Enantioselective Reduction of Configurationally Unstable Biaryl Hydroxy Aldehydes - A Novel Approach to Axially Chiral Biaryls
  作者：Gerhard Bringmann、Matthias Breuning

  DOI：10.1055/s-1998-1728

  日期：1998.6

  The oxazaborolidine-assisted atropo-enantioselective catecholborane reduction of configurationally unstable biaryl hydroxy aldehydes to axially chiral biaryl alcohols by (dynamic) kinetic resolution is achieved in enantiomeric ratios (er) of up to 92:8. Using the same chiral auxiliary, the M- or, optionally, the P-configurated atropisomer can be obtained in good er's - just by variation of the relative quantity of the achiral reductant. This hints at the existence of two competing reaction pathways with opposite asymmetric inductions. The enantiomeric ratios observed strongly depend on the relative steric demand of the substituents ortho to the biaryl axis.

  在噁唑硼烷辅助下，通过（动态）动力学解析将构型不稳定的双芳基羟基醛还原成轴向手性双芳基醇的邻苯二酚硼烷对映体选择性还原，对映体比（er）可达 92:8。使用相同的手性助剂，只需改变非手性还原剂的相对数量，就能以较好的对映体比（er's）获得 M-或 P-配置的异构体。这表明存在着两种具有相反不对称诱导作用的竞争反应途径。观察到的对映体比率在很大程度上取决于双芳基轴正向取代基的相对立体需求。
• The Atropo-Enantioselective Ring Opening of Achiral Lactone-Bridged Biaryls Using Chirally Modified Aluminum Hydrides
  作者：Gerhard Bringmann、Thomas Hartung

  DOI：10.1055/s-1992-26126

  日期：——

  The atropo-enantioselective preparation of the chiral biaryl 2-hydroxymethyl-1-(2-hydroxy-4, 6-dimethoxyphenyl)naphthalene (7) from 1,3-dimethoxy-6H-benzo [b]naphtho[1,2-d]pyran-6-one (3) is described, whereby two formal problems of stereoselective biaryl synthesis are independently solved: The carbon-carbon bond formation by the intramolecular aryl coupling of the ester-type prefixed aromatic halves, and the asymmetric induction at the pre-formed biaryl axis by the subsequent stereoselective ring-opening reaction, using chiral hydrogen nucleophiles.

  本研究描述了从 1,3 二甲基氧-6H-苯并 [b]萘并[1,2-d]吡喃-6-酮 (3) 手性 2-羟甲基-1-(2-羟基-4, 6-二甲氧基苯基)萘 (7) 的异丙烯-对映体选择性制备方法，从而独立解决了立体选择性双芳基合成的两个形式问题：利用手性氢亲核物，通过酯型预固定芳香半边的分子内芳基偶联形成碳-碳键，并通过随后的立体选择性开环反应在预形成的双芳基轴上进行不对称诱导。
• NHC-Catalyzed Chemo- and Enantioselective Reaction between Aldehydes and Enals for Access to Axially Chiral Arylaldehydes
  作者：Zhiguo Zheng、Qian Liu、Xiaolin Peng、Zhichao Jin、Jian Wu

  DOI：10.1021/acs.orglett.3c04189

  日期：2024.2.2

  A chiral carbene-catalyzed chemo- and enantioselective reaction with racemic biaryl aldehydes and α-bromoenals is developed for access to axially chiral 2-arylbenzaldehydes through atroposelective dynamic kinetic resolution (DKR) processes. This atroposelective DKR strategy can tolerate a broad scope of substrates with diverse functionalities. The axially chiral 2-aryl benzaldehyde products generally

  开发了一种手性卡宾催化的与外消旋联芳醛和 α-溴烯醛的化学和对映选择性反应，用于通过对映选择性动态动力学拆分 (DKR) 过程获得轴向手性 2-芳基苯甲醛。这种肌细胞选择性 DKR 策略可以耐受具有不同功能的广泛底物。轴向手性2-芳基苯甲醛产物通常具有中等至良好的产率和对映选择性。当前方法提供的轴向手性分子可通过简单的变换而变化，以提供具有优异光学纯度的轴向手性功能分子。
• Biaryl hydroxy aldehydes as intermediates in the metal-assisted atropo-enantioselective reduction of biaryl lactones: Structures and aldehyde-lactol equilibria
  作者：Gerhard Bringmann、Matthias Breuning、Heike Endress、Daniel Vitt、Karl Peters、Eva-Maria Peters

  DOI：10.1016/s0040-4020(98)00618-8

  日期：1998.9

  The synthesis of substituted 1-(2'-hydroxyphenyl)naphthalene-2-carbaldehydes 4 and 6-alkoxy-6H-pyrans 7 and 8, analogs of the postulated metallated intermediates in the atropo-enantioselective ring cleavage of configuratively unstable biaryl lactones 2, is described. While the equilibria between the open hydroxy aldehydes 4 and the cyclic lactol structures 3 are completely shifted towards 4 for the derivatives 4c-g with substituents ortho to the biaryl axis, the lactol forms are the dominating structures (ca. 50-100%) for the ortho-unsubstituted compounds. For the lactols 3 and their acetalic analogs 6, 7, and 8, those diastereomeric conformations are preferred (77-100%) that have the exo-oxygen function axial. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Atropo-enantioselective biaryl synthesis by stereocontrolled cleavage of configuratively labile lactone-bridged precursors using chiral H-nucleophiles
  作者：G Bringmann

  DOI：10.1016/s0040-4020(01)88014-5

  日期：1993.9.3

  The atropo-enantioselective synthesis of axially stereogenic, sterically shielded biaryl systems is described, by stereocontrolled ring opening of the corresponding lactone-bridged, still configurationally labile precursors. The atropenantiomer excesses range up to 97% ee.