5-fluoro-2-(naphthalen-1-yl)benzaldehyde | 1400812-87-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 5-fluoro-2-(naphthalen-1-yl)benzaldehyde
• 英文别名: 5-Fluoro-2-naphthalen-1-ylbenzaldehyde；5-fluoro-2-naphthalen-1-ylbenzaldehyde
• CAS: 1400812-87-4
• 化学式: C₁₇H₁₁FO
• 分子量: 250.272
• InChiKey: GQZHTIZQESOQQG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  5-fluoro-2-(naphthalen-1-yl)benzaldehyde 在 Ag[1-closo-CB11H6Cl6] 、 [PtCl₃(P(C₃(NMe₂)2)3)](perchlorate)2 、 potassium carbonate 作用下， 以 甲醇 、 1,2-二氯乙烷 为溶剂， 生成 3-fluoro BPh
  参考文献：
  名称：

  Exploiting the π-Acceptor Properties of Carbene-Stabilized Phosphorus Centered Trications [L₃P] ³⁺: Applications in Pt(II) Catalysis

  摘要：

  Reaction of tris(dimethylaminocyclopropenium) substituted phosphine 1 with K2PtCl4 afforded the bench stable complex 3 which upon treatment with Ag[CB11H6Cl6] turned out to be an excellent catalyst for the transformation of a variety of ortho-biaryl substituted alkynes into polycyclic homo- and heteroarenes of different size, shape, and curvature through a 6-endo-dig cyclization. This constitutes the first example ever reported of using a P-1-centered trication as ligand in catalysis. The strong pi-acceptor character of 1 that derives from its three positive charges substantially increases the intrinsic pi-acidity of Pt in complex 1.PtCl2 and dramatically enhances its ability to activate pi-systems toward nucleophilic attack. As a consequence, a remarkable acceleration of the model transformation is observed when compared with other classical pi-acceptor ligands such as P(OPh)(3) or P(C6F5)(3). Moreover, the employment of 1 as ligand also expands the scope of this reaction to previously inaccessible substitution patterns. Kinetic studies and deuterium labeling experiments as well as density functional theory (DFT) calculations were performed in order to explain these findings.

  DOI：

  10.1021/ja306947m
• 作为产物：
  描述：

  1-萘硼酸 、 2-溴-5-氟苯甲醛 在 四(三苯基膦)钯 、 sodium carbonate 作用下， 以 乙二醇二甲醚 、 水 为溶剂， 反应 12.0h， 生成 5-fluoro-2-(naphthalen-1-yl)benzaldehyde
  参考文献：
  名称：

  通过消除P-O催化Pd催化的对映选择性C-H烯丙基化：轴向手性联芳基的合成

  摘要：

  联芳基阻转异构体在天然产物，药物和非对称合成中非常重要。这些具有完整对映体控制和高度多样性的手性支架的有效合成仍然具有挑战性。本文报道的是Pd催化的对映选择性C-H烯丙基化，叔亮氨酸是一种有效的催化手性瞬态助剂。通过β-O消除，制备了多种对映体富集的联芳基醛，具有合成上有用的产率，并具有出色的对映体选择性（最高> 99％ee）。该反应可以以克为单位进行，而不会侵蚀ee价值。可以高对映体纯度获得各种​​轴向手性羧酸。所得的轴向手性联芳基醛和羧酸可以作为手性配体和/或有机催化剂用于不对称合成中。

  DOI：

  10.1002/anie.201811256

文献信息

• Scalable, Stereocontrolled Formal Syntheses of (+)-Isoschizandrin and (+)-Steganone: Development and Applications of Palladium(II)-Catalyzed Atroposelective C−H Alkynylation
  作者：Gang Liao、Qi-Jun Yao、Zhuo-Zhuo Zhang、Yong-Jie Wu、Dan-Ying Huang、Bing-Feng Shi

  DOI：10.1002/anie.201713106

  日期：2018.3.26

  unique structure based on an axially chiral biaryl moiety as well as their significant biological activity. Herein, we describe the development of a palladium‐catalyzed atroposelective C−H alkynylation and its application in gram‐scale, stereocontrolled formal syntheses of (+)‐isoschizandrin and (+)‐steganone. tert‐Leucine was identified as an efficient, catalytic transient chiral auxiliary. A wide

  二苯并环辛二烯木脂素是一类有趣的分子，因为它们基于轴向手性联芳基部分的独特结构以及显着的生物学活性。在本文中，我们描述了钯催化的对映选择性C-H炔基化的发展及其在（+）-异五味子和（+）-甾烷酮的克级立体控制形式合成中的应用。叔亮氨酸被认为是一种高效的催化瞬态手性助剂。通过这种方法，可以以良好的收率（高达99％ee）和良好的收率（高达99％）制备各种对映体富集的联芳基化合物 。
• Pd‐Catalyzed Atroposelective C−H Allylation through β‐O Elimination: Diverse Synthesis of Axially Chiral Biaryls
  作者：Gang Liao、Bing Li、Hao‐Ming Chen、Qi‐Jun Yao、Yu‐Nong Xia、Jun Luo、Bing‐Feng Shi

  DOI：10.1002/anie.201811256

  日期：2018.12.21

  Biaryl atropisomers are of great importance in natural products, pharmaceuticals, and asymmteric synthesis. The efficient synthesis of these chiral scaffolds with full enantiocontrol and high diversity remains challenging. Reported herein is a Pd‐catalyzed atroposelective C−H allylation with tert‐leucine as an efficient catalytic chiral transient auxiliary. A wide range of enantioenriched biaryl aldehydes

  联芳基阻转异构体在天然产物，药物和非对称合成中非常重要。这些具有完整对映体控制和高度多样性的手性支架的有效合成仍然具有挑战性。本文报道的是Pd催化的对映选择性C-H烯丙基化，叔亮氨酸是一种有效的催化手性瞬态助剂。通过β-O消除，制备了多种对映体富集的联芳基醛，具有合成上有用的产率，并具有出色的对映体选择性（最高> 99％ee）。该反应可以以克为单位进行，而不会侵蚀ee价值。可以高对映体纯度获得各种​​轴向手性羧酸。所得的轴向手性联芳基醛和羧酸可以作为手性配体和/或有机催化剂用于不对称合成中。
• Pd-Catalyzed Atroposelective C–H Acyloxylation Enabling Access to an Axially Chiral Biaryl Phenol Organocatalyst
  作者：Jitan Zhang、Jian Fan、Yehe Wu、Ziyi Guo、Jiaping Wu、Meihua Xie

  DOI：10.1021/acs.orglett.2c01981

  日期：2022.7.22

  the Pd(II)-catalyzed atroposelective C–H acyloxylation strategy for the assembly of biaryl aldehyde atropoisomers using readily available amino acids as the catalytic auxiliary and chiral pool. This strategy exhibits a broad substrate scope with a good yield (≤90%) and excellent enantioselectivity (≤99%), furnishing functionalized aldehydes through direct asymmetric C–H oxidation. The application utility

  在此，我们提出了 Pd(II) 催化的阻转选择性 C-H 酰氧基化策略，该策略使用容易获得的氨基酸作为催化助剂和手性池来组装联芳醛阻转异构体。该策略表现出广泛的底物范围，具有良好的产率（≤90%）和优异的对映选择性（≤99%），通过直接不对称 C-H 氧化提供官能化醛。通过简明合成一种阻转异构氨基苯酚有机催化剂证明了该方法的应用价值，该催化剂在催化二乙基锌与醛的不对称加成反应中具有良好的对映控制。
• Chiral Transient Ligand Enabled Enantioselective Synthesis of Atropisomers Decorated with Unactivated Olefins via a Palladium-Catalyzed C–H Olefination
  作者：Vadivel Arjun、Masilamani Jeganmohan

  DOI：10.1021/acs.orglett.3c02721

  日期：2023.10.27

  Herein, atroposelective synthesis of axially chiral biaryls with unactivated olefins by a palladium-catalyzed C–H olefination using a chiral transient directing group strategy has been disclosed. This protocol is well compatible with a variety of biaryl-2-aldehydes as well as various olefins such as allyl sulfonamides and allyl sulfones to provide the atroposelective olefinated products in synthetically

  在此，公开了使用手性瞬态导向基团策略通过钯催化的C-H烯化反应用未活化的烯烃对轴向手性联芳基进行旋转选择性合成。该方案与各种联芳基-2-醛以及各种烯烃（例如烯丙基磺酰胺和烯丙基砜）良好相容，以合成有用的收率提供对映选择性烯化产物，其优异的对映选择性高达>99% ee。此外，通过产品的简单多样化合成了多种轴向手性联芳醇，具有优异的对映选择性。
• Exploiting the π-Acceptor Properties of Carbene-Stabilized Phosphorus Centered Trications [L₃P] ³⁺: Applications in Pt(II) Catalysis
  作者：Javier Carreras、Mahendra Patil、Walter Thiel、Manuel Alcarazo

  DOI：10.1021/ja306947m

  日期：2012.10.10

  Reaction of tris(dimethylaminocyclopropenium) substituted phosphine 1 with K2PtCl4 afforded the bench stable complex 3 which upon treatment with Ag[CB11H6Cl6] turned out to be an excellent catalyst for the transformation of a variety of ortho-biaryl substituted alkynes into polycyclic homo- and heteroarenes of different size, shape, and curvature through a 6-endo-dig cyclization. This constitutes the first example ever reported of using a P-1-centered trication as ligand in catalysis. The strong pi-acceptor character of 1 that derives from its three positive charges substantially increases the intrinsic pi-acidity of Pt in complex 1.PtCl2 and dramatically enhances its ability to activate pi-systems toward nucleophilic attack. As a consequence, a remarkable acceleration of the model transformation is observed when compared with other classical pi-acceptor ligands such as P(OPh)(3) or P(C6F5)(3). Moreover, the employment of 1 as ligand also expands the scope of this reaction to previously inaccessible substitution patterns. Kinetic studies and deuterium labeling experiments as well as density functional theory (DFT) calculations were performed in order to explain these findings.