(3,5-dimethoxylphenyl)lithium | 905280-34-4

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: (3,5-dimethoxylphenyl)lithium
• 英文别名: 3,5-dimethoxyaryllithium；1-lithium-3,5-dimethoxybenzene
• CAS: 905280-34-4
• 化学式: C₈H₉LiO₂
• 分子量: 144.099
• InChiKey: WKQZFJHOISTABH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.04
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3,5-dimethoxylphenyl)lithium 在 戴斯-马丁氧化剂 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 0.17h， 生成 cyclohepten-1-yl-(3,5-dimethoxyphenyl)methanone
  参考文献：
  名称：

  Photo-Nazarov反应：范围和应用

  摘要：

  研究了芳基乙烯基酮的光-纳扎罗夫反应的反应条件和范围。与传统的酸催化方法相比，这种光解电环化反应在中性或碱性条件下进行。用紫外线（254 nm）照射带有各种芳族环，酸敏感基团，环己烯基，环庚烯基和不饱和吡喃的底物，可以平稳地产生六氢芴酮及其相关结构。这种光-纳扎罗夫反应也可能适用于在烯酮上带有β-烷基的底物，该底物产生了相应的含有季中心的多环。这些光电循环产物可能被证明可用于合成多种天然产物及其衍生物。

  DOI：

  10.1002/chem.201402993

文献信息

• Enantioselective Copper(I)-Catalyzed Alkynylation of Oxocarbenium Ions to Set Diaryl Tetrasubstituted Stereocenters
  作者：Srimoyee Dasgupta、Thomas Rivas、Mary P. Watson

  DOI：10.1002/anie.201507373

  日期：2015.11.16

  An enantioselective, copper(I)-catalyzed addition of terminal alkynes to isochroman ketals to set diaryl, tetrasubstituted stereocenters has been developed. The success of this reaction relies on identification of a Cu/PyBox catalyst capable of distinguishing the faces of the diaryl-substituted oxocarbenium ion. This challenging transformation enables efficient conversion of readily available, racemic

  已经开发了对映选择性铜（I）催化的末端炔烃加到异色满缩酮中以固定二芳基，四取代的立体中心。该反应的成功取决于鉴定能够区分二芳基取代的氧碳鎓离子的表面的Cu / PyBox催化剂。这种具有挑战性的转化可以将容易获得的外消旋缩酮高效转化为具有完全取代的立体异构中心的高价值对映体富集的异色满产品。对于各种异色铬酮缩酮和一系列炔烃，观察到高收率和对映体过量。
• Primary α-tertiary amine synthesis <i>via</i> α-C–H functionalization
  作者：Dhananjayan Vasu、Angel L. Fuentes de Arriba、Jamie A. Leitch、Antoine de Gombert、Darren J. Dixon

  DOI：10.1039/c8sc05164j

  日期：——

  A quinone-mediated general synthetic platform for the construction of primary α-tertiary amines from abundant primary α-branched amine starting materials is described. This procedure pivots on the efficient in situ generation of reactive ketimine intermediates and subsequent reaction with carbon-centered nucleophiles such as organomagnesium and organolithium reagents, and TMSCN, creating quaternary

  描述了一种醌介导的通用合成平台，用于从丰富的伯 α-支化胺起始材料构建伯 α-叔胺。该过程的重点是有效地原位生成反应性酮亚胺中间体，并随后与碳中心亲核试剂（例如有机镁和有机锂试剂以及 TMSCN）反应，产生四元中心。此外，扩展到反极性光氧化还原催化可以通过亲核α-氨基自由基中间体与亲电子试剂发生反应。这种高效、广泛适用且可扩展的胺对胺合成平台已成功应用于库和 API 合成以及药物分子的功能化。
• Radical-polar crossover reactions of vinylboron ate complexes
  作者：Marvin Kischkewitz、Kazuhiro Okamoto、Christian Mück-Lichtenfeld、Armido Studer

  DOI：10.1126/science.aal3803

  日期：2017.3.3

  substituent to a metal catalyst en route to carbon-carbon bond formation. Kischkewitz et al. report a metal-free alternative pathway, wherein the boron stays bound to one end of the olefin while a carbon radical attacks the other end. Charge transfer then prompts migration of an alkyl or aryl group from the boron to form a second carbon-carbon bond. The boron can subsequently be displaced, generating a

  硼编排双重反应 在广泛使用的 Suzuki 偶联反应中，硼在形成碳-碳键的过程中将烯烃取代基交给金属催化剂。Kischkewitz 等人。报告了一种不含金属的替代途径，其中硼保持与烯烃的一端结合，而碳自由基攻击另一端。然后电荷转移促使烷基或芳基从硼迁移以形成第二个碳-碳键。随后硼可以被置换，从简单的前体生成一系列多功能的醇、内酯和季碳中心。科学，这个问题 p。936 硼通过连续的自由基和极性序列编排了两个碳-碳键的形成。乙烯基硼酸酯是铃木-宫浦交叉偶联反应的重要底物。然而，硼取代的烯烃作为自由基受体很少受到关注，乙烯基硼酸酯配合物的自由基化学研究不足。我们在这里展示了碳自由基有效地添加到乙烯基硼酸酯复合物中，并且它们的加合物自由基阴离子经历自由基极性交叉：从硼到 α-碳 sp2 中心的 1,2-烷基/芳基转移提供仲或叔烷基硼酸酯。与 Suzuki-Miyaura 偶联相反，不需要过渡金属，
• A Study on Zr–Ir Multiple Bonding Active for C–H Bond Cleavage
  作者：Masataka Oishi、Masato Oshima、Hiroharu Suzuki

  DOI：10.1021/ic500258g

  日期：2014.7.7

  Zr-Ir hydrido complexes with ansa-(cyclopentadienyl)-(amide) as the supporting ligand in the zirconium fragment, e.g., ((LZrR)-Zr-1)(Cp*Ir)(mu-H)(3) [L-1 = Me2Si(eta(5)-C5Me4)((NBu)-Bu-t), R = Cl (5), Ph (7), Me (10), alkyl, and aryl] were designed, synthesized, and isolated as tractable early late heterodinuclear complexes. Despite the presence of the three supporting hydride ligands, Zr-Ir distances in the crystal structures of 5, alkyl, and aryl complexes [2.74-2.76 angstrom] were slightly longer than the sum of the element radii of Zr and Ir [2.719 angstrom]. These hydrocarbyl complexes displayed the thermolytic C H activation of a variety of aromatic compounds and several organometallic compounds. Also, the substrate scope and limitation in the Zr Ir system were studied. The regiochemical outcomes during the C H activation of pyridine derivatives and methoxyarenes suggested the in situ generation of a Lewis acidic active intermediate, i.e., ((LZr)-Zr-1)(Cp*IrH2) (III). The existence of III and relevant a-complex intermediates (LZr)-Zr-1(eta(2)-R-H)}(Cp*IrH2) (IIR) (R = Me, Ph) in the ligand exchange was demonstrated by the direct isolation of a Et3PO-adduct of III (39b) from 7 and kinetic studies. The structure of the direct Zr-Ir bonds in IIph, IIMe, III, and 39b were probed using computational studies. The unprecedented strong M-M' interactions in the early-late heterobimetallic (ELHB) complexes have been proposed herein.
• Diarylmethyl substituted titanocenes: Promising anti-cancer drugs
  作者：Clara Pampillón、Oscar Mendoza、Nigel J. Sweeney、Katja Strohfeldt、Matthias Tacke

  DOI：10.1016/j.poly.2006.01.007

  日期：2006.7

  From the reaction of tert-butyl lithium with p-bromo-N,N-dimethylaniline (1a), p-bromoanisole (1b) or 1-bromo-3,5-dimethoxybenzene (1c), p-N,N-dimethylanityl lithium (2a), p-anisyl lithium (2b) or (3,5-dimethoxyphenyl) lithium (2c), respectively, were obtained. When reacted with 6-(p-N,N-dimethylanilinyl)fulvene (3a), 6-(p-methoxyphenyl)fulvene (3b) or 3,5-(dimethoxyphenyl)fulvene (3c), the corresponding lithiated intermediates were formed (4a-c). Titanium tetrachloride was added "in situ", obtaining titanocenes 5a-C, respectively. When these titanocenes were tested against pig kidney carcinoma (LLC-PK) cells, inhibitory concentrations (IC50) Of 3.8 x 10(-5) M, 4.5 x 10(-5) M, and 7.8 x 10(-5) M, respectively, were observed. These values represent improved cytotoxicity against LLC-PK, compared to their ansa-analogues. (c) 2006 Elsevier Ltd. All rights reserved.