2-Methyl-2-(trimethylsiloxy)cyclopropancarbonsaeure-methylester | 77903-43-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2-Methyl-2-(trimethylsiloxy)cyclopropancarbonsaeure-methylester
• 英文别名: methyl 2-methyl-2-trimethylsiloxycyclopropane carboxylate；Methyl 2-methyl-2-trimethylsiloxycyclopropanecarboxylate；Methyl 2-methyl-2-trimethylsilyloxycyclopropane-1-carboxylate
• CAS: 77903-43-6
• 化学式: C₉H₁₈O₃Si
• 分子量: 202.326
• InChiKey: DUWMKAXFMSBNLZ-UHFFFAOYSA-N

物化性质

• 沸点：
  186.5±33.0 °C(Predicted)
• 密度：
  0.98±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.79
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-Methyl-2-(trimethylsiloxy)cyclopropancarbonsaeure-methylester 在 palladium on activated charcoal 氢气 作用下， 以 四氢呋喃 为溶剂， 反应 21.0h， 以85%的产率得到乙酰丙酸甲酯
  参考文献：
  名称：

  Brueckner, Christiane; Reissig, Hans-Ulrich, Chemische Berichte, 1987, vol. 120, p. 617 - 626

  摘要：

  DOI：
• 作为产物：
  描述：

  重氮乙酸甲酯 、 2-(三甲基硅氧基)丙烯 、 copper;(Z)-4-oxopent-2-en-2-olate;(E)-4-oxopent-2-en-2-olate 以70%的产率得到
  参考文献：
  名称：

  KUNKEL, E.;REICHELT, I.;REISSIG, H. -H., LIEBIGS ANN. CHEM., 1984, N 3, 512-530

  摘要：

  DOI：

文献信息

• Stereoselective synthesis of tricyclic compounds by intramolecular palladium-catalyzed addition of aryl iodides to carbonyl groups
  作者：Jakub Saadi、Christoph Bentz、Kai Redies、Dieter Lentz、Reinhold Zimmer、Hans-Ulrich Reissig

  DOI：10.3762/bjoc.12.118

  日期：——

  process that stereoselectively led to bi- and tricyclic compounds in moderate to excellent yields. Four X-ray crystal structure analyses unequivocally defined the structure of crucial cyclization products. The relative configuration of the precursor compounds is essentially transferred to that of the products and the formed hydroxy group in the newly generated cyclohexane ring is consistently in trans-arrangement

  从具有邻碘苄基的γ-酮酸酯开始，我们研究了钯催化的环化过程，该过程立体选择性地产生了中等至极好的收率的双环和三环化合物。四种X射线晶体结构分析明确定义了关键环化产物的结构。前体化合物的相对构型基本上转移到产物的相对构型，并且新生成的环己烷环中形成的羟基相对于甲氧基羰基始终处于反式排列。提出了一种过渡态模型来解释观察到的立体化学结果。该钯催化的Barbier型反应需要将钯（II）还原回到钯（0），这显然是通过本发明的三乙胺实现的。
• Highly substituted benzannulated cyclooctanol derivatives by samarium diiodide-induced cyclizations
  作者：Jakub Saadi、Irene Brüdgam、Hans-Ulrich Reissig

  DOI：10.3762/bjoc.6.141

  日期：——

  This systematic study reveals that steric and electronic factors exhibited by the alkene and ketone subunits are of high importance for the outcome of these cyclization reactions leading to highly substituted benzannulated cyclooctanol derivatives. In exceptional cases, 7-exo-trig cyclizations to cycloheptanol derivatives have been observed. In examples with high steric hindrance the ketyl-aryl coupling

  一系列被各种苯乙烯亚单元适当取代的 γ-氧代酯经历了二碘化钐诱导的 8-endo-trig 环化。这些通过钐羰基的反应的效力、区域选择性和立体选择性在很大程度上取决于被攻击的烯烃部分的取代模式。中间体有机钐质子化的立体选择性也受底物结构特征的影响。这项系统研究表明，烯烃和酮亚基表现出的空间和电子因素对于这些环化反应的结果非常重要，这些环化反应导致高度取代的苯并环辛醇衍生物。在特殊情况下，已观察到 7-exo-trig 环化成环庚醇衍生物。
• A novel rearrangement leading to methoxycarbonylmethylated silyl enol ethers
  作者：Hans-Ulrich Reissig

  DOI：10.1016/s0040-4039(00)98693-3

  日期：1985.1

  Methyl 2-siloxycyclopropanecarboxylates rearrange smoothly and quantitatively to the corresponding silyl enol ethers (3) by addition of a catalytical amount of iodo trimethylsilane. Scope and limitation of this novel process as well as the synthesis of the electron rich diene (10a) are described.

  通过加入催化量的碘代三甲基硅烷，将2-甲硅烷氧基环丙烷甲酸甲酯平稳而定量地重排为相应的甲硅烷基烯醇醚（3）。描述了该新颖方法的范围和局限性以及富电子二烯（10a）的合成。
• Siloxycyclopropanes in Ugi Four-Component Reaction: A New Method for the Synthesis of Highly Substituted Pyrrolidinone Derivatives
  作者：Reinhold Zimmer、Antje Ziemer、Margit Gruner、Irene Brüdgam、Hans Hartl、Hans-Ulrich Reissig

  DOI：10.1055/s-2001-16762

  日期：——

  Reaction of methyl trimethylsiloxycyclopropanecarboxylates 3 with amino acids, tert-butylisonitrile and methanol furnished amino diacid derivatives 2 as the result of an Ugi 5-center 4-component reaction. This one-pot reaction involves β-formyl esters such as 1 as intermediate, which are liberated in situ. Adducts 2 could be thermally cyclized to provide γ-lactams 4 in good yields. The multi component reaction was combined with this cyclization process to a fairly efficient one-pot procedure. Thus, cyclopropane derivative 3a was converted into γ-lactam 4a in good yield. Two of the γ-lactams 4 were reduced with lithium aluminum hydride to give pyrrolidine derivatives 5. Based on an X-ray analysis of the major diastereomer of compound 5d, the diastereoselectivity of the 4-component reaction is discussed.

  三甲基硅氧烷环丙烷羧酸甲酯 3 与氨基酸、叔丁基异腈和甲醇反应生成氨基二酸衍生物 2，这是 Ugi 5-中心 4-组分反应的结果。这种单锅反应以δ-甲酰基酯（如 1）为中间体，并在原位释放。加合物 2 可通过热环化反应生成δ-内酰胺 4，产率很高。多组分反应与这种环化过程相结合，形成了一种相当有效的单锅程序。因此，环丙烷衍生物 3a 以良好的收率转化为 δ³ 内酰胺 4a。用氢化铝锂还原其中两个δ-内酰胺 4，得到吡咯烷衍生物 5。根据对化合物 5d 主要非对映异构体的 X 射线分析，讨论了 4 组分反应的非对映选择性。
• Low temperature equilibration of cyclopropanes by Lewis acid catalysis
  作者：Hans-Ulrich Reissig、Ingrid Böhm

  DOI：10.1016/s0040-4039(00)81506-3

  日期：1983.1

  Under the influence of Lewis acids the cis/trans-equilibration of methyl 2-trimethyl-siloxy cyclopropanecarboxylates occurs even at −78°C. It involves the heterolytic cleavage of a CC bond and seems to be governed by steric effects.

  在路易斯酸的影响下，即使在-78°C时，也会发生2-三甲基-甲硅烷氧基环丙烷甲酸甲酯的顺式/反式平衡。它涉及CC键的杂合裂解，似乎受空间效应支配。