magnesium,2-methylbut-2-ene,chloride | 35189-96-9

• 物质功能分类: 化学试剂 - 有机试剂 - 烯烃（环状与无环状）
• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: magnesium,2-methylbut-2-ene,chloride
• 英文别名: 3-methyl-2-butenylmagnesium chloride；(3-methylbut-2-en-1-yl)magnesium chloride；3,3-Dimethyl-2-propenylmagnesium chloride；chlorure de methyl-3 buten-2 ylmagnesium；γ-methylcrotylmagnesium chloride；3-methyl-butenyl-(2)-magnesiumchloride；3-methylbut-2-enylmagnesium chloride
• CAS: 35189-96-9
• 化学式: C₅H₉ClMg
• 分子量: 128.884
• InChiKey: LICPNZOGRCGBTL-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  2.23
• 重原子数：
  7.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  magnesium,2-methylbut-2-ene,chloride 在 dilithium tetrachlorocuprate 、 氨 、 三氯化铁 、 lithium 作用下， 以 四氢呋喃 、 乙醚 、 溶剂黄146 为溶剂， 反应 1.08h， 生成 辅酶Q10
  参考文献：
  名称：

  Transformation of ubiquinone-9 into ubiquinone-10 by the cuprate version of the Wurtz reaction at the key stage

  摘要：

  DOI：

  10.1007/bf00978441
• 作为产物：
  描述：

  1-氯-3-甲基-2-丁烯 在 magnesium 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 生成 magnesium,2-methylbut-2-ene,chloride
  参考文献：
  名称：

  Reactivity of unsaturated sultones synthesized from unsaturated alcohols by ring-closing metathesis. Application to the racemic synthesis of the originally proposed structure of mycothiazole

  摘要：

  Unsaturated sultones have been synthesized from various primary or secondary alkenols by ring-closing metathesis of the corresponding unsaturated sulfonates. By treatment with a strong base, beta,gamma-unsaturated sultones can be metalated and subsequently alkylated with electrophiles. When iodomethylmagnesium chloride was selected as the electrophile, seven-membered ring beta,gamma-unsaturated sultones were converted into homoallylic conjugated (Z)-dienols. This methodology was applied to the racemic synthesis of the originally proposed structure of the marine natural product mycothiazole. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.07.010
• 作为试剂：
  描述：

  magnesium,2-methylbut-2-ene,chloride 、 (2R,3S,4S)-3-[tert-butyl(dimethyl)silyl]oxy-2,4-dimethyl-7-phenylmethoxyheptanal 在 magnesium,2-methylbut-2-ene,chloride 作用下， 以76的产率得到(5R,6S,7S)-10-(benzyloxy)-6-(tert-butyldimethylsilyloxy)-3,3,5,7-tetramethyldec-1-en-4-one
  参考文献：
  名称：

  伊沙匹隆全合成

  摘要：

  本发明属于药物合成技术领域，具体涉及一种伊沙匹隆的中间体、全合成方法以及用途。该化合物具有如下结构式1： 。

  公开号：

  CN103275091A

文献信息

• Allylation of Carbonyl Compounds with Allylic Gallium Reagents
  作者：Takashi Tsuji、Shin-ichi Usugi、Hideki Yorimitsu、Hiroshi Shinokubo、Seijiro Matsubara、Koichiro Oshima

  DOI：10.1246/cl.2002.2

  日期：2002.1

  Allylic gallium reagents, prepared from gallium trichloride and the corresponding allylic Grignard reagents, allylated carbonyl compounds in good yields in an aqueous medium as well as in organic solvent.

  烯丙基镓试剂，由三氯化镓与相应的烯丙基格氏试剂制备而来，在水中及有机溶剂中均能以良好产率使羰基化合物发生烯丙基化反应。
• A Catalytic Approach for Enantioselective Synthesis of Homoallylic Alcohols Bearing a <i>Z</i>-Alkenyl Chloride or Trifluoromethyl Group. A Concise and Protecting Group-Free Synthesis of Mycothiazole
  作者：Ryan J. Morrison、Farid W. van der Mei、Filippo Romiti、Amir H. Hoveyda

  DOI：10.1021/jacs.9b11178

  日期：2020.1.8

  catalytic processes and is expected to facilitate the preparation of bioactive organic molecules. More specifically, Z-chloro-substituted allylic pinacolatoboronate is first obtained through stereoretentive cross-metathesis between Z-crotyl-B(pin) (pin = pinacolato) and Z-dichloroethene, both of which are commercially available. The organoboron compound may be used in the central transformation of the entire

  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
• Photochemical 1,3-stannyl rearrangement of allylic stannanes
  作者：Akio Takuwa、Takashi Kanaue、Koichi Yamashita、Yutaka Nishigaichi

  DOI：10.1039/a707609f

  日期：——

  The photochemical 1,3-stannyl rearrangement of allylic stannanes has been investigated. The photorearrangement of (E)-cinnamyl(triphenyl)stannane is not observed in benzene under anaerobic conditions, while the photoinduced 1,3-stannyl migration takes place in the same solvent under aerobic conditions, or in the presence of organic halides or a radical-trapping agent to give a photoequilibrium mixture of the cinnamylstannane and its branched regioisomer, 1-phenylprop-2-enyl(triphenyl)stannane, with the latter predominating. Cinnamyl(trialkyl)stannanes and their homologues also afford the corresponding branched allylstannanes under similar photochemical conditions. These 1,3-stannyl migrations proceed intramolecularly via cinnamyl π-π* excitation in competition with homolytic (cinnamyl)C–Sn bond fission. In contrast, the 1,3-stannyl migration of crotyl- and prenyl-(tributyl)stannanes is not efficient, but their triphenyl or dibutylphenyl derivatives undergo the 1,3-rearrangement via excitation of the phenyl group(s) on the tin atom to give a regioisomeric mixture of the starting linear tin compounds and the branched ones with the former predominating.

  对烯丙基锡烷的光化学1,3-锡重排进行了研究。在无氧条件下，(E)-肉桂基(三苯基)锡烷在苯中未观察到光重排现象，而在有氧条件下或有有机卤化物或自由基捕获剂存在时，在同一溶剂中发生光诱导的1,3-锡迁移，形成肉桂基锡烷及其支链区域异构体、1-苯基丙-2-烯基(三苯基)锡烷的光平衡混合物，后者占主导地位。肉桂基(三烷基)锡烷及其类似物在类似的光化学条件下也得到相应的支链烯丙基锡烷。这些1,3-锡迁移通过肉桂基π-π*激发的分子内过程进行，与均裂的(肉桂基)C–Sn键断裂竞争。相比之下，巴豆基和烯丙基(三丁基)锡烷的1,3-锡迁移效率不高，但其三苯基或二丁基苯基衍生物通过锡原子上的苯基团激发发生1,3-重排，得到起始线性锡化合物和支链锡化合物的区域异构体混合物，前者占主导地位。
• Addition von organomagnesium-verbindungen an nicht aktivierte CC-doppelbindungen. II
  作者：H. Lehmkuhl、D. Reinehr

  DOI：10.1016/s0022-328x(00)88665-9

  日期：1972.1

  Organomagnesium compounds with allylic double bonds (aliyl-, methallyl- and crotylmagnesium halides and octadienediylmagnesium) react with 1,2-dienes (allene) or 1,3-dienes (butadiene, isoprene) to yield cyclohexane derivatives. Compounds of the crotylmagnesium type add predominantly in the isomeric α-methylallyl form. In addition alkylmagnesium halides with tertiary or secondary alkyl groups show

  具有烯丙基双键的有机镁化合物（卤代烷基，甲代烯丙基和巴豆基卤化镁和辛二烯基镁）与1,2-二烯（丙二烯）或1,3-二烯（丁二烯，异戊二烯）反应生成环己烷衍生物。巴豆基镁类型的化合物主要以异构体α-甲基烯丙基形式添加。另外，具有叔或仲烷基的烷基卤化镁显示出对烯烃的增强的反应性。
• ONE-STEP SYNTHESIS OF HOMOTERPENOIC CARBOXYLIC ACIDS FROM β-ISOPROPENYL-β-PROPIOLACTONE AND ORGANOCOPPER REAGENTS
  作者：Tamotsu Fujisawa、Toshio Sato、Masatoshi Kawashima、Masakuni Nakagawa

  DOI：10.1246/cl.1981.1307

  日期：1981.9.5

  Regioselective reaction of Grignard reagents in the presence of a copper(I) catalyst or of organocuprates with the terminal vinyl carbon of β-isopropenyl-β-propiolactone through the SN2′ pathway affords 4-methyl-3-alkenoic acids in which the (E)-isomers predominate in good yields. Synthetic utility of this reaction is demonstrated in one-step synthesis of homoterpenoic carboxylic acids.

  在铜 (I) 催化剂或有机铜酸盐存在下，格氏试剂与 β-异丙烯基-β-丙内酯的末端乙烯基碳通过 SN2' 途径发生区域选择性反应，得到 4-甲基-3-链烯酸，其中 (E )-异构体以良好的产率占优势。该反应的合成效用在高萜羧酸的一步合成中得到证明。