magnesium,iodomethane,chloride | 4776-37-8

• 分子结构分类: 有机化合物 - 有机卤素化合物
• 英文名称: magnesium,iodomethane,chloride
• 英文别名: (iodomethyl)magnesium chloride；iodomethylmagnesium chloride；iodomethyl-magnesium chloride；Iodmethylmagnesiumchlorid
• CAS: 4776-37-8
• 化学式: CH₂ClIMg
• 分子量: 200.689
• InChiKey: CAEWAENQMJNBCO-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.24
• 重原子数：
  4.0
• 可旋转键数：
  1.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  2-{1-[3-(3,3-dimethoxypropyl)-2,2-dioxo-2,3,6,7-tetrahydro-2λ⁶-[1,2]oxathiepin-7-yl]-1-methylethyl}-4-((2E)-hexa-2,5-dienyl)thiazole 、 magnesium,iodomethane,chloride 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.75h， 以60%的产率得到(5Z)-2-[(4-(2E)-hexa-2,5-dienyl)thiazol-2-yl]-10,10-dimethoxy-2-methyl-7-methylenedec-5-en-3-ol
  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
• 作为产物：
  描述：

  二碘甲烷 在 异丙基氯化镁 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 1.0h， 生成 magnesium,iodomethane,chloride
  参考文献：
  名称：

  新的磺内酯串联反应

  摘要：

  已经开发了新的一锅法，用于磺基磺酸盐的合成精制和伴随的脱硫。通过去质子化，自由基环化/过渡金属化或共轭1，6-加成与碘甲基氯化镁进行烷基化制备的α-金属化烯丙基磺内酯，随后立即进行β-消除反应，即可得到高度取代的无硫亚甲基环己烯。几个1,10-合成中的高级中间体开环-eudesmanolides是由这种新的方法有效地可用。

  DOI：

  10.1016/s0040-4039(98)01743-2

文献信息

• Total Synthesis of the Microtubule Stabilizing Antitumor Agent Laulimalide and Some Nonnatural Analogues:  The Power of Sharpless' Asymmetric Epoxidation
  作者：Anjum Ahmed、E. Kate Hoegenauer、Valentin S. Enev、Martin Hanbauer、Hanspeter Kaehlig、Elisabeth Öhler、Johann Mulzer

  DOI：10.1021/jo026743f

  日期：2003.4.1

  With (R,R)-tartrate the 16,17-epoxide laulimalide (1) is formed selectively, whereas (S,S)-tartrate generates the 21,22-epoxide 142. This demonstrates the high reagent control involved in the SAE process, which in this case is used to achieve high stereo- and regioselectivity. Laulimalide and some derivatives thereof have been tested with respect to antitumor activity and compared to standard compounds

  描述了三种合成脱氧月桂酰亚胺（3）的途径，这是海洋海绵代谢产物laulimalide（1）的直接前体。这些路线的主要区别在于其闭环步骤。因此，路线1使用Still-Gennari烯化，路线2使用山口内酯化，路线3使用分子内的烯丙基硅烷-醛加成以建立大环结构。将未保护的脱氧衍生物3进行Sharpless′不对称环氧化（SAE）。酒石酸（R，R）选择性地形成16,17-环氧十二烷基苯磺酸（1），而酒石酸（S，S）-酒石酸生成21,22-环氧142。这表明SAE过程涉及较高的试剂控制，在这种情况下，可用于实现较高的立体选择性和区域选择性。
• An Intramolecular Case of Sharpless Kinetic Resolution: Total Synthesis of Laulimalide
  作者：Johann Mulzer、Elisabeth Öhler

  DOI：10.1002/1521-3773(20011015)40:20<3842::aid-anie3842>3.0.co;2-r

  日期：2001.10.15

  skeleton was assembled by means of Julia-Kocienski (C16-C17) and Horner-Wadsworth-Emmons (C21-C22) olefinations. Still-Gennari olefination was used for the C2-C3 ring closure. The key step of the synthesis was a regioselective C16-C17 matched Sharpless asymmetric epoxidation.

  通过新的合成途径获得了微管稳定的抗肿瘤药劳力美利德（1）。碳骨架是通过Julia-Kocienski（C16-C17）和Horner-Wadsworth-Emmons（C21-C22）烯烃组装而成的。Still-Gennari烯烃化反应用于C2-C3闭环。合成的关键步骤是区域选择性的C16-C17匹配的Sharpless不对称环氧化。
• Studies toward the Synthesis of Spirolide C: Exploration into the Formation of the 23-Membered All-Carbon Macrocyclic Framework
  作者：Craig E. Stivala、Zhenhua Gu、Lindsay L. Smith、Armen Zakarian

  DOI：10.1021/ol203342e

  日期：2012.2.3

  The synthesis of two complex subunits en route to spirolide C is described. A key alkyllithium addition to an aldehyde joins the fragments, which are advanced in order to investigate a ring-closing metathesis to form the 23-membered all-carbon macrocyclic framework.

  描述了合成螺内酯 C 途中的两个复杂亚基。醛的关键烷基锂加成连接了碎片，这些碎片被推进以研究闭环复分解以形成 23 元全碳大环骨架。
• Spongistatin synthetic studies. 3. Construction of the C(1–17) spiroketal
  作者：Amos B. Smith、Quyan Lin、Kiyoshi Nakayama、Armen M. Boldi、Christopher S. Brook、Mark D. McBriar、William H. Moser、Masao Sobukawa、Linghang Zhuang

  DOI：10.1016/s0040-4039(97)10501-9

  日期：1997.12

  A convergent synthesis of the C(1–17) AB-ring subunit of the spongistatins, exceedingly scarce and highly antimitotic polyether macrolides, has been achieved via a one-flask dithiane bisalkylation, stereocontrolled spiroketalization, and Julia sulfone coupling/methylenation.

  海绵状抑制素的C（1-17）AB环亚基的聚合合成，极其稀少且高度抗有丝分裂的聚醚大环内酯类化合物，是通过单烧瓶二噻吩双烷基化，立体控制的螺缩酮化和Julia砜偶联/甲基化来实现的。
• Desulfurization of sultams with simultaneous methylenation
  作者：Victor O. Rogachev、Sandra Merten、Tobias Seiser、Olga Kataeva、Peter Metz

  DOI：10.1016/j.tetlet.2007.10.153

  日期：2008.1

  Alkylation of gamma- and delta-sultams with (iodomethyl)trimethylsilane followed by treatment of the resultant silanes with tetrabutylammonium fluoride gave rise to sulfur-free unsaturated amines. In particular, N-THP substituted sultams were found to be useful substrates for the alkylation event. A corresponding one-pot transformation involving sultam alpha-alkylation with (iodomethyl)magnesium chloride is also reported. (c) 2007 Elsevier Ltd. All rights reserved.