zinc dimethoxide | 1184-55-0

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: zinc dimethoxide
• 英文别名: zinc(II) methoxide；zinc methoxide；Dimethoxyzink；zinc;methanolate
• CAS: 1184-55-0
• 化学式: C₂H₆O₂Zn
• 分子量: 127.458
• InChiKey: HXGUOSGJKUCORR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.03
• 重原子数：
  3
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  23.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  丙基溴化镁 、 zinc dimethoxide 以 乙醚 为溶剂， 生成 di-n-propyl zinc
  参考文献：
  名称：

  Remarkably Robust Monomeric Alkylperoxyzinc Compounds from Tris(oxazolinyl)boratozinc Alkyls and O₂

  摘要：

  Metal alkylperoxides are remarkable, highly effective, yet often thermally unstable, oxidants that may react through a number of possible pathways including O-O homolytic cleavage, M-O homolytic cleavage, nucleophilic O-atom transfer, and electrophilic O-atom transfer. Here we describe a series of zinc alkyl compounds of the type To(M)ZnR (To(M) = tris(4,4-dimethyl-2-oxazolinyl)phenylborate; R = Et, n-C3H7, i-C3H7, t-Bu) that react with O-2 at 25 degrees C to form isolable monomeric alkylperoxides To(M)ZnOOR in quantitative yield. The series of zinc alkylperoxides is crystallographically characterized, and the structures show systematic variations in the Zn-O-O angle and O-O distances. The observed rate law for the reaction of To(M)ZnEt (2) and O-2 is consistent with a radical chain mechanism, where the rate-limiting S(H)2 step involves the interaction of (OOR)-O-center dot and To(M)ZnR. In contrast, To(M)ZnH and To(M)ZnMe are unchanged even to 120 degrees C under 100 psi of O-2 and in the presence of active radical chains (e.g., (OOEt)-O-center dot). This class of zinc alkylperoxides is unusually thermally robust, in that the compounds are unchanged after heating at 120 degrees C in solution for several days. Yet, these compounds are reactive as oxidants with phosphines. Additionally, an unusual alkylperoxy group transfer to organosilanes affords To(M)ZnH and ROOSiR3'.

  DOI：

  10.1021/ja303440n
• 作为产物：
  描述：

  [((1,1,1-trifluoro-2-((2,6-diisopropylphenyl)amido)-4-((2,6-diethylphenyl)imino)-2-penteneato)Zn(μ-OMe))2Zn(μ-OMe)2] 以 甲苯 为溶剂， 以0%的产率得到zinc dimethoxide
  参考文献：
  名称：

  Structure and reactivity of mono- and dinuclear diiminate zinc alkyl complexes

  摘要：

  The synthesis, structure and reactivity of several diiminate ligands are presented. The syntheses of five representative beta-diiminate (BDI) zinc alkyl complexes and one beta-oxo-delta-diiminate (BODDI) zinc alkyl are described. BDI ligands with varying backbone and N-aryl substituents display different solid state structures. [(BDI)ZnR] are synthesized by the reaction of (BDI)H with ZnR, in quantitative yield. Previously reported (BDI-1)ZnEt is a three-coordinate monomer in the solid state whereas [(BDI-3)ZnEt](infinity) [(BDI-3) = 2-((2,6-diisopropylphenyl)amido)-3-cyano-4-((2,6-diisopropylphenyl)imino-2-pentene] and [(BDI-4)ZnEt](infinity) [(BDI-4) = 2-((2,6-diethylphenyl)amido)-3-cyano-4-((2,6-diethylphenyl)imino-2-pentene] form one dimensional coordination polymers. The bimetallic complex [(BODDI-1)(ZnEt)(2)] [(BODDI-1) = 2,6-bis((2,6-diisopropylphenyl)amido)-2,5-heptadien-4-one] is prepared through the reaction of (BODDI-1)H-2 with two equivalents ZnEt2. Both [(BDI)ZnEt] and [(BODDI)ZnEt] complexes react with acetic acid to give the acetate complexes in moderate to high yields, offering a superior synthetic route to these complexes. [(BDI)ZnR] [BDI=(BDI-3) or 1,1,1-trifluoro-2-((2,6-diisopropylphenyl)amido)-4-((2,6-diethylphenyl)imino-2-pentene), (BDI-5)] complexes react with MeOH to produce [{(BDI)Zn(mu-OMe)}(2)Zn(mu-OMe)(2)] in moderate yields. The molecular structures of [(BDI-3)ZnEt], [(BDI-4)ZnEt], [(BODDI-1)(ZnEt)(2)], [(BODDI-1)Zn-2(mu-OAc)(2)], [{(BDI-3)Zn(mu-OMe)}(2)Zn(mu-OMe)(2)] and [{(BDI-5)Zn(mu-OMe)}(2)Zn(mu-OMe)2] have been determined by X-ray diffraction. (C) 2003 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(03)00544-8
• 作为试剂：
  描述：

  3-甲酰基吲哚酸-1-羧酸 t-丁基酯 、 (Z)-2-(3-chloroallyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 在 甲醇 、 (2S)-2-((2-hydroxy-3-(triphenylsilyl)benzyl)amino)-2-(3-hydroxyadamantan-1-yl) 1-(isoindolin-2-yl)ethan-1-one 、 zinc dimethoxide 作用下， 以 甲苯 为溶剂， 反应 14.0h， 以96%的产率得到tert-butyl (R,Z)-3-(4-chloro-1-hydroxybut-3-en-1-yl)-1H-indole-1-carboxylate
  参考文献：
  名称：

  一种对映选择性合成带有 Z-链烯基氯或三氟甲基的高烯丙醇的催化方法。一种简洁且无保护基团的霉噻唑合成方法

  摘要：

  针对非对映选择性和对映选择性路线提出了一种无保护基团策略，可用于制备多种 Z-高烯丙醇，其效率明显高于其他可行方法。该方法需要合并几个催化过程，并有望促进生物活性有机分子的制备。更具体地说，Z-氯取代的烯丙基频哪醇硼酸酯首先通过 Z-巴豆基-B(pin) (pin = pinacolato) 和 Z-二氯乙烯之间的立体保留交叉复分解获得，这两种物质都可商购获得。有机硼化合物可用于整个方法的中心转化，即由质子活化的手性氨基苯酚硼基催化剂催化的醛的α-和对映选择性加成。然后催化交叉偶联可以以高对映体纯度提供所需的 Z-高烯丙醇。烯烃复分解步骤可以使用底物和可购买的基于 Mo 的复合物进行。第二个催化步骤所需的氨基苯酚化合物可以从廉价的起始材料以数克的量制备。还可以以类似的高效率和区域选择性、非对映选择性和对映选择性制备大量带有 Z-F3C 取代烯烃的高烯丙醇。此外，虽然α-选择性和对映选择性稍低，但可以以相似的效率获得三取代的

  DOI：

  10.1021/jacs.9b11178

文献信息

• Exploring Electrochemical C(sp³)–H Oxidation for the Late-Stage Methylation of Complex Molecules
  作者：Luiz F. T. Novaes、Justin S. K. Ho、Kaining Mao、Kaida Liu、Mayank Tanwar、Matthew Neurock、Elisia Villemure、Jack A. Terrett、Song Lin

  DOI：10.1021/jacs.1c09412

  日期：2022.1.26

  targets containing basic nitrogen groups that are prevalent in medicinally active agents. When combined with organozinc-mediated C–C bond formation, our protocol enabled the direct methylation of a myriad of amine derivatives including those that have previously been explored for the “magic methyl” effect. This synthesis strategy thus circumvents multistep de novo synthesis that is currently necessary to

  “神奇的甲基”效应，通过掺入单个甲基来显着提高生物活性化合物的效力，为药物化学家在药物发现过程中采用的简单而强大的策略提供了一种简单而强大的策略。尽管取得了重大进展，但能够对结构复杂的药物进行选择性 C(sp 3 )–H 甲基化的方法仍然非常有限。在这项工作中，我们公开了一种通过电化学氧化对受保护胺（即酰胺、氨基甲酸酯和磺酰胺）进行α-甲基化的模块化、高效和选择性策略。机理分析指导我们在经典的Shono氧化反应的基础上开发了一种改进的电化学方案，该反应具有反应范围广、官能团兼容性高、操作简单等特点。重要的是，该反应系统适合于药物活性剂中常见的含有碱性氮基团的复杂靶标的后期功能化。当与有机锌介导的 C-C 键形成相结合时，我们的方案能够实现多种胺衍生物的直接甲基化，包括那些先前已探索过的“神奇甲基”效应。因此，这种合成策略规避了目前获得此类化合物所必需的多步骤从头合成，并且有可能加速药物发现工作。
• The Cyclopropane Ring as a Reporter of Radical Leaving-Group Reactivity for Ni-Catalyzed C(sp³)–O Arylation
  作者：L. Reginald Mills、John J. Monteith、Gabriel dos Passos Gomes、Alán Aspuru-Guzik、Sophie A. L. Rousseaux

  DOI：10.1021/jacs.0c06904

  日期：2020.7.29

  understand and predict reactivity is highly important for the development of new reactions. In the context of Ni-catalyzed C(sp3)-O functionalization, we have developed a unique strategy employing activated cyclopropanols to aid the design and optimization of a redox-active leaving group for C(sp3)-O arylation. In this chemistry, the cyclopropane ring acts as a reporter of leaving-group reactivity, since the

  理解和预测反应性的能力对于新反应的发展非常重要。在 Ni 催化的 C(sp3)-O 官能化的背景下，我们开发了一种独特的策略，采用活化的环丙醇来帮助设计和优化用于 C(sp3)-O 芳基化的氧化还原活性离去基团。在该化学中，环丙烷环充当离去基团反应性的报告分子，因为在极性 (2e) 条件下获得开环产物，而在自由基 (1e) 条件下获得闭环产物。机理研究表明，最佳离去基团具有氧化还原活性，并且与 Ni(I)/Ni(III) 催化循环一致。优化的反应条件还用于合成许多芳基环丙烷，它们是有价值的药物基序。
• Synthesis and characterisation of trigonal C2-chiral di- and tetra-substituted bis(oxazoline) alkyl zinc complexes and their reactivity towards protic reagents
  作者：Erwan Le Roux、Nicolas Merle、Karl W. Törnroos

  DOI：10.1039/c0dt01252a

  日期：——

  “uncontrolled”, the formation of homoleptic four-coordinate compounds are favoured (2a–b), but not for the more sterically crowded ligand (c). The zinc-ethyl derivatives (1a–c) react readily with protic reagents such as acetic acid (HOAc) and methanol (MeOH). For compounds 1a–c a redistribution of ligands is observed leading preferentially to homoleptic compounds, except for the bulkier ligand c providing

  一系列锌（II）由稳定的烷基配合物c ^ 2 -手性双恶唑啉配体（[R 1，R 2中，其中R 1 =（4小号） -吨卜，R 2 = H（一个）; R 1 =（4 S）-Ph，R 2 = H（b）； R 1 =（4 R）-Ph，R 2 =（5 S）-Ph（c）），已经合成并在结构上表征。（R 1，R 2 BOX）H配体与ZnEt反应2英寸甲苯以高收率得到（R 1，R 2 BOX）ZnEt，1a，1b和1c的三配位化合物。但是，当“不受控制”在ZnEt 2上添加（BOX）H配体（a–b）时，倾向于形成均配的四配位化合物（2a–b），但对于空间更拥挤的配体（c）。锌-乙基衍生物（1a–c）与质子试剂如醋酸 （HOAc）和 甲醇 （甲醇）。对于化合物1a-c，观察到配体的重新分布优先导致均化化合物，除了较大的配体c提供了三坐标的复合物，被鉴定为（Ph，Ph BOX）Zn（OMe），4c。的反应乙酰
• Lithium BINOL Phosphate Catalyzed Desymmetrization of <i>meso</i>-Epoxides with Aromatic Thiols
  作者：Gajendrasingh Ingle、Michael G. Mormino、Jon C. Antilla

  DOI：10.1021/ol502527q

  日期：2014.11.7

  A highly enantioselective method for desymmetrization of meso-epoxides using thiols is reported. This is the first example of epoxide activation achieved using metal BINOL phosphates. The reaction has a broad scope in terms of epoxide substrates and aromatic thiol nucleophiles. The resulting beta-hydroxyl sulfides are obtained in excellent yield and enantioselectivity.
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: B: SVol.1, 4.8.5, page 226 - 230
  作者：

  DOI：——

  日期：——