methyl 4-oxo-2-(2-trimehylsilylethynylbenzyl)pentanoate | 224568-44-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: methyl 4-oxo-2-(2-trimehylsilylethynylbenzyl)pentanoate
• 英文别名: Methyl 4-oxo-2-[[2-(2-trimethylsilylethynyl)phenyl]methyl]pentanoate
• CAS: 224568-44-9
• 化学式: C₁₈H₂₄O₃Si
• 分子量: 316.472
• InChiKey: RCGYKZOFDGQMEH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.23
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 4-oxo-2-(2-trimehylsilylethynylbenzyl)pentanoate 在 六甲基磷酰三胺 、 tin(II) iodide 、 potassium carbonate 、 叔丁醇 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 17.0h， 生成 methyl 8-hydroxy-8-methyl-5,6,7,8-tetrahydrobenzocyclooctene-6-carboxylate
  参考文献：
  名称：

  Competition between Novel 8- endo-dig and 6- trig Cyclizations of Samarium Ketyls Leading either to Benzannulated Cyclooctene or to Hexahydronaphthalene Derivatives

  摘要：

  Ketoesters 3a-3h with an alkynylaryl substituent were prepared by standard methods starting from siloxycyclopropanes 6a and 6b. Their reactions with 2.2 equiv. of samarium diiodide in the presence of hexamethyl phosphoramide either produced benzannulated cyclooctenol derivatives 4b (or lactone 9), 4f, 4g, and 4h or hexahydronaphthalene derivatives 5a, 5c, and 5d. The competition between 8-endo-dig and 6-trig cyclizations strongly depends on the substitution pattern of 3. Plausible explanations for this competition and of the diastereoselectivity observed are presented in this paper. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)00353-7
• 作为产物：
  描述：

  methyl 2-(o-iodobenzyl)-4-oxo-pentanoate 、 三甲基乙炔基硅 在 bis-triphenylphosphine-palladium(II) chloride copper(l) iodide 、 二乙胺 作用下， 以87%的产率得到methyl 4-oxo-2-(2-trimehylsilylethynylbenzyl)pentanoate
  参考文献：
  名称：

  Competition between Novel 8- endo-dig and 6- trig Cyclizations of Samarium Ketyls Leading either to Benzannulated Cyclooctene or to Hexahydronaphthalene Derivatives

  摘要：

  Ketoesters 3a-3h with an alkynylaryl substituent were prepared by standard methods starting from siloxycyclopropanes 6a and 6b. Their reactions with 2.2 equiv. of samarium diiodide in the presence of hexamethyl phosphoramide either produced benzannulated cyclooctenol derivatives 4b (or lactone 9), 4f, 4g, and 4h or hexahydronaphthalene derivatives 5a, 5c, and 5d. The competition between 8-endo-dig and 6-trig cyclizations strongly depends on the substitution pattern of 3. Plausible explanations for this competition and of the diastereoselectivity observed are presented in this paper. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)00353-7

文献信息

• A New Samarium Diiodide Induced Reaction: Intramolecular Attack of Ketyl Radical Anions on Aryl Substituents with Formation of 1,4-Cyclohexadiene Derivatives
  作者：Chimmanamada U. Dinesh、Hans-Ulrich Reissig

  DOI：10.1002/(sici)1521-3773(19990315)38:6<789::aid-anie789>3.0.co;2-w

  日期：1999.3.15

  Beware of samarium diiodide and aryl ketones! If the ketyl radical anion which is formed by electron transfer finds a properly placed aryl group, a highly diastereoselective cyclization may occur. After the transfer of a second electron and protonation bi- and polycyclic products with a common 1,4-cyclohexadiene moiety may be isolated [Eq. (a)]. X=CHCO2 R, NCH2 Ph; HMPA=(Me2 N)3 PO.

  当心二碘化and和芳基酮！如果通过电子转移形成的酮基自由基阴离子找到适当放置的芳基，则可能发生高度非对映选择性的环化反应。在第二电子转移和质子化之后，可以分离具有共同的1，4-环己二烯部分的双环和多环产物[式2]。（一种）]。X = CHCO 2 R，NCH 2 Ph; HMPA =（Me 2 N）3 PO。
• Competition between Novel 8- endo-dig and 6- trig Cyclizations of Samarium Ketyls Leading either to Benzannulated Cyclooctene or to Hexahydronaphthalene Derivatives
  作者：Erathodiyil Nandanan、Chimmanamada U Dinesh、Hans-Ulrich Reissig

  DOI：10.1016/s0040-4020(00)00353-7

  日期：2000.6

  Ketoesters 3a-3h with an alkynylaryl substituent were prepared by standard methods starting from siloxycyclopropanes 6a and 6b. Their reactions with 2.2 equiv. of samarium diiodide in the presence of hexamethyl phosphoramide either produced benzannulated cyclooctenol derivatives 4b (or lactone 9), 4f, 4g, and 4h or hexahydronaphthalene derivatives 5a, 5c, and 5d. The competition between 8-endo-dig and 6-trig cyclizations strongly depends on the substitution pattern of 3. Plausible explanations for this competition and of the diastereoselectivity observed are presented in this paper. (C) 2000 Elsevier Science Ltd. All rights reserved.