methyl 5-methyl-4-oxo-2-(2-ethynylbenzyl)hexanoate | 224568-42-7

• 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 5-methyl-4-oxo-2-(2-ethynylbenzyl)hexanoate
• 英文别名: Methyl 2-[(2-ethynylphenyl)methyl]-5-methyl-4-oxohexanoate
• CAS: 224568-42-7
• 化学式: C₁₇H₂₀O₃
• 分子量: 272.344
• InChiKey: OTRDKLHLAXVTTE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  20
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.41
• 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 5-methyl-4-oxo-2-(2-ethynylbenzyl)hexanoate 在 samarium diiodide 、 叔丁醇 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 为溶剂， 反应 4.0h， 以41%的产率得到methyl 8-hydroxy-8-isopropyl-5,6,7,8-tetrahydrobenzocyclooctene-6-carboxylate
  参考文献：
  名称：

  一种新的二碘化Sa诱导的反应：烷基自由基阴离子对芳基取代基的分子内攻击，形成1,4-环己二烯衍生物。

  摘要：

  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。

  DOI：

  10.1002/(sici)1521-3773(19990315)38:6<789::aid-anie789>3.0.co;2-w
• 作为产物：
  描述：

  methyl 2-(2-iodobenzyl)-5-methyl-4-oxopentanoate 在 bis-triphenylphosphine-palladium(II) chloride copper(l) iodide 、 四丁基氟化铵 、 二乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 methyl 5-methyl-4-oxo-2-(2-ethynylbenzyl)hexanoate
  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.
• Samarium Diiodide in the Synthesis of Medium-Sized Rings - Carbocycles and Heterocycles by Intramolecular Addition of Samarium Ketyls to Alkynes
  作者：Hans-Ulrich Reissig、Alexandra Hölemann

  DOI：10.1055/s-2004-835657

  日期：——

  A series of alkynyl-substituted ketones and aldehydes was subjected to samarium diiodide in the presence of HMPA to study the scope and limitations of their ketyl-alkyne coupling. Seven- and eight-membered heterocycles such as 4, 6, 8, 25, 27, 29, 33, and 35 could be isolated in moderate to good yields. Other cyclization products were isolated in low yields only. The efficacy of the reductive cyclization

  在 HMPA 存在下，对一系列炔基取代的酮和醛进行二碘化钐处理，以研究其炔基-炔偶联的范围和局限性。七元和八元杂环如 4、6、8、25、27、29、33 和 35 可以以中等至良好的产率分离。其他环化产物仅以低产率分离。还原环化的效果很大程度上取决于取代模式以及炔烃和羰基之间的间隔基中杂原子和/或苯环的存在。azocine 29 的第一次后续转化导致烯酮 38 或环氧化物 39 证明了该方法的合成潜力。