4,4-dimethyl-5-phenyldimethylsilylmethyl-5-hexen-2-one | 620176-32-1

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 4,4-dimethyl-5-phenyldimethylsilylmethyl-5-hexen-2-one
• 英文别名: 5-[[Dimethyl(phenyl)silyl]methyl]-4,4-dimethylhex-5-en-2-one
• CAS: 620176-32-1
• 化学式: C₁₇H₂₆OSi
• 分子量: 274.478
• InChiKey: YTIAKQHEHLAFEO-UHFFFAOYSA-N

物化性质

• 沸点：
  369.8±35.0 °C(Predicted)
• 密度：
  0.91±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.16
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4,4-dimethyl-5-phenyldimethylsilylmethyl-5-hexen-2-one 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 2.33h， 生成 2,2,4-trimethyl-4-[1-(dimethylphenylsilylmethyl)cyclopropyl]pentan-1-ol
  参考文献：
  名称：

  Seven-Membered Ring Formation from Cyclopropanated Oxo- and Epoxyallylsilanes

  摘要：

  A useful strategy for cycloheptane annulations from oxo- and epoxyallylsilanes, prepared by silylcupration of allenes, has been developed, and their application to the stereoselective synthesis of 4-methylenecycloheptan-1-ols is of great potential in the construction of seven-membered ring natural products presented.

  DOI：

  10.1021/jo200705u
• 作为产物：
  描述：

  4-甲基-3戊烯-2-酮 、 丙二烯 、 phenyldimethylsilylcopper 在 锂丁酯 、 三氟化硼乙醚 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以90%的产率得到4,4-dimethyl-5-phenyldimethylsilylmethyl-5-hexen-2-one
  参考文献：
  名称：

  酸催化的环氧烯丙基硅烷环化反应。一个异常的重排环化过程。

  摘要：

  [反应：请参见文字]。据报道，合成带有苯基二甲基甲硅烷基的环氧烯丙基硅烷的新途径涉及甲硅烷基化丙二烯，将共轭物加成烯酮以及硫代叶立德介导的环氧化。呈现了路易斯酸催化的这些底物的环化。没有观察到源自5-exo和/或6-endo攻击的预期正常产物；而是形成了由串联重排-环化过程产生的亚甲基环己醇。

  DOI：

  10.1021/ol035297v

文献信息

• Synthesis of 3-Methylenecyclohexan-1-ols by Lewis Acid Catalyzed Cyclization of (Epoxy-allyl)silanes
  作者：Francisco J. Pulido、Asunción Barbero、Pilar Castreño

  DOI：10.1002/ejoc.200901263

  日期：2010.3

  A new route for the synthesis of (epoxy-allyl)silanes bearing the PhMe 2 Si group has been developed and their acid-catalyzed cyclization studied. The so-called normal products derived from 5-exo or 6-endo attack were never obtained. On the contrary, an interesting tandem rearrangement/cyclization process was observed, which selectively led to 3-methylenecyclohexan-1-ols. A mechanism is proposed to

  已经开发了一种合成带有 PhMe 2 Si 基团的（环氧-烯丙基）硅烷的新途径，并研究了它们的酸催化环化。5-exo 或 6-endo 攻击衍生的所谓正常产物从未得到过。相反，观察到了一个有趣的串联重排/环化过程，它选择性地产生了 3-亚甲基环己-1-醇。提出了一种机制来解释这种串联反应。环化过程的立体选择性取决于催化剂的性质。
• One-Pot Synthesis of 2,7-Dioxabicyclo[2.2.1]heptanes from Oxoallylsilanes
  作者：Francisco J. Pulido、Asunción Barbero、Raquel Abad

  DOI：10.1002/ejoc.201101087

  日期：2011.12

  oxoallylsilanes is described. The mechanism of this tandem reaction is a sequential epoxidation of the allylsilane moiety and subsequent intramolecular cyclization. This simple protocol allows the synthesis of epoxy-bridged tetrahydropyrans from allene in two high-yielding steps: silylcupration of allene (followed by capture of the intermediate cuprate with enones) and treatment of the oxoallylsilanes thus obtained

  描述了从氧代烯丙基硅烷合成甲硅烷基化 2,7-二氧杂双环 [2.2.1] 庚烷的一锅法高产率合成方法。这种串联反应的机理是烯丙基硅烷部分的顺序环氧化和随后的分子内环化。这个简单的协议允许在两个高产步骤中从丙二烯合成环氧桥连四氢吡喃：丙二烯的甲硅烷基铜化（随后用烯酮捕获中间铜酸盐）和用 MCPBA 处理由此获得的氧代烯丙基硅烷。然而，在相同条件下，氧乙烯基硅烷以非常立体选择性的方式产生环氧甲硅烷基酮。
• Efficiency of Acid- and Mercury-Catalyzed Cyclization Reactions in the Synthesis of Tetrahydrofurans from Allylsilyl Alcohols
  作者：Francisco J. Pulido、Asunción Barbero、Patricia Val、Alberto Diez、Alfonso González-Ortega

  DOI：10.1002/ejoc.201200666

  日期：2012.9

  The scope of the acid-catalyzed and mercury-catalyzed cyclization reactions of allylsilyl alcohols is described. This methodology has been found to be an efficient approach to the synthesis of highly substituted tetrahydrofurans. The stereoselectivity of the cyclization is dependent both on the substitution of the starting alcohol and on the catalyst. A plausible mechanism has been proposed that is

  描述了烯丙基甲硅烷醇的酸催化和汞催化环化反应的范围。已发现该方法是合成高度取代的四氢呋喃的有效方法。环化的立体选择性取决于起始醇的取代和催化剂。已经提出了一种与结果一致的合理机制。
• Spiro-Cyclopropanation from Oxoallylsilanes
  作者：Asunción Barbero、Pilar Castreño、Francisco J. Pulido

  DOI：10.1021/ja051967b

  日期：2005.6.1

  A novel highly stereoselective spiro-cyclopropanation reaction from oxoallylsilanes is described. Oxoallylsilanes are readily obtained by silylcupration of allene followed by conjugate addition to enones. The former oxoallylsilanes undergo a tandem cyclization-cyclopropanation reaction when treated with CH2I2/Me3Al, leading to hydroxylated polycyclic systems bearing the spiro-cyclopropane moiety. The scope of the process is studied, and a feasible pathway is discussed.
• Acid-Catalyzed Cyclization of Epoxyallylsilanes. An Unusual Rearrangement Cyclization Process
  作者：Asunción Barbero、Pilar Castreño、Francisco J. Pulido

  DOI：10.1021/ol035297v

  日期：2003.10.1

  synthesis of epoxyallylsilanes bearing the phenyldimethylsilyl group is reported that involves silylcupration of allene, conjugate addition to enones, and sulfur-ylide-mediated epoxidation. The Lewis acid-catalyzed cyclization of these substrates is presented. The expected normal products derived from 5-exo and/or 6-endo attack are not observed; instead, methylenecyclohexanols resulting from a tandem rea

  [反应：请参见文字]。据报道，合成带有苯基二甲基甲硅烷基的环氧烯丙基硅烷的新途径涉及甲硅烷基化丙二烯，将共轭物加成烯酮以及硫代叶立德介导的环氧化。呈现了路易斯酸催化的这些底物的环化。没有观察到源自5-exo和/或6-endo攻击的预期正常产物；而是形成了由串联重排-环化过程产生的亚甲基环己醇。