allyldimethylbenzhydrylsilane | 274676-28-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: allyldimethylbenzhydrylsilane
• 英文别名: allylbenzhydryldimethylsilane；Benzhydryl-dimethyl-prop-2-enylsilane
• CAS: 274676-28-7
• 化学式: C₁₈H₂₂Si
• 分子量: 266.458
• InChiKey: UXSRVEQIPBYVFT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.25
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  allyldimethylbenzhydrylsilane 在 lithium aluminium tetrahydride 、 四氯化锡 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 0.34h， 生成 (2R*,4S*)-4-benzhydryldimethylsilyl-2-hydroxymethyl-2-phenyltetrahydrofuran
  参考文献：
  名称：

  Benzhydryldimethylsilyl Allylic Silanes:  Syntheses and Applications to [3 + 2] Annulation Reactions

  摘要：

  A new silyl group, the benzhydryldimethylsilyl group, has been developed that is easily synthesized and that undergoes facile oxidation. The [3 + 2] annulation reactions of allylic silanes with this silyl group provide a variety of highly substituted five-membered carbocycles and heterocycles with high stereoselectivities. The silyl groups of these cyclic compounds have been oxidized to hydroxyl groups to demonstrate the general synthetic utility of the method.

  DOI：

  10.1021/ol005676d
• 作为产物：
  描述：

  烯丙基二甲基氯硅烷 、 二苯基甲烷 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 32.0h， 以82%的产率得到allyldimethylbenzhydrylsilane
  参考文献：
  名称：

  Benzhydryldimethylsilyl Allylic Silanes:  Syntheses and Applications to [3 + 2] Annulation Reactions

  摘要：

  A new silyl group, the benzhydryldimethylsilyl group, has been developed that is easily synthesized and that undergoes facile oxidation. The [3 + 2] annulation reactions of allylic silanes with this silyl group provide a variety of highly substituted five-membered carbocycles and heterocycles with high stereoselectivities. The silyl groups of these cyclic compounds have been oxidized to hydroxyl groups to demonstrate the general synthetic utility of the method.

  DOI：

  10.1021/ol005676d

文献信息

• Catalytic Enantioselective Carboannulation with Allylsilanes
  作者：Nicolas R. Ball-Jones、Joseph J. Badillo、Ngon T. Tran、Annaliese K. Franz

  DOI：10.1002/anie.201403607

  日期：2014.9.1

  scandium(III)/indapybox complex with tetrakis‐[3,5‐bis(trifluoromethyl)phenyl]‐borate (BArF) to enhance catalytic activity and control stereoselectivity. Functionalized cyclopentanes containing a quaternary carbon center are derived from alkylidene oxindole, coumarin, and malonate substrates with high stereoselectivity. The enantioselective 1,4‐conjugate addition and enantioselective lactone formation

  介绍了第一个与烯丙基硅烷的催化不对称碳环化。使用钪 (III)/indapybox 配合物与四-[3,5-双(三氟甲基)苯基]-硼酸盐 (BArF) 催化对映选择性 [3+2] 环化，以提高催化活性并控制立体选择性。含有季碳中心的官能化环戊烷衍生自具有高立体选择性的亚烷基羟吲哚、香豆素和丙二酸酯底物。还描述了对映选择性 1,4-共轭加成和对映选择性内酯形成（通过捕获 β-甲硅烷基碳正离子）。
• Electrophilic Fluorocyclization of Allyl Silanes
  作者：Susan C. Wilkinson、Oscar Lozano、Marie Schuler、Maria C. Pacheco、Roger Salmon、Véronique Gouverneur

  DOI：10.1002/anie.200901795

  日期：2009.9.7

  A refreshing cascade: General fluorocyclization reactions will breathe new life into the use of fluorinated hetero‐ and carbocycles as pharmaceuticals and agrochemicals. Allyl silanes have now been shown to undergo fluorination–cyclization with NF reagents to give cis‐ and trans‐substituted fluorinated heterocycles selectively (see scheme). The correct choice of silyl group was critical to prevent

  令人耳目一新的层叠：普通的氟环化反应将为氟化杂合和碳环化合物作为药物和农用化学品的使用注入新的活力。现在烯丙基硅烷已显示出经过氟化环有N  ˚F试剂给予顺-和反式选择性取代含氟杂环化合物（见方案）。正确选择甲硅烷基对防止竞争性氟代脱甲硅烷基化至关重要。
• Tin(IV) Chloride Catalyzed Cycloaddition Reactions between 3-Ethoxycyclobutanones and Allylsilanes
  作者：Jun-ichi Matsuo、Shun Sasaki、Takaya Hoshikawa、Hiroyuki Ishibashi

  DOI：10.1021/ol901329c

  日期：2009.9.3

  Formal [4 + 2] cycloaddition between various 3-ethoxycyclobutanones and allyltrialkylsilanes proceeded to give 3-ethoxy-5-[(trialkylsilyl)methyl]cyclohexan-1-ones by catalysis with tin(VI) chloride. The use of allyl-tert-butyldiphenylsilane induced 1,5-hydride transfer, which gave 2-[3-(tert-butyldiphenylsilyl)propyl]-6-methyltetrahydro-4-pyrones.

  各种3-乙氧基环丁酮与烯丙基三烷基硅烷之间的正式[4 + 2]环加成反应通过用氯化锡（VI）催化得到3-乙氧基-5-[（三烷基甲硅烷基）甲基]环己-1-酮。烯丙基叔丁基二苯基硅烷的使用引起1，5-氢化物转移，得到2- [3-（叔丁基二苯基甲硅烷基）丙基] -6-甲基四氢-4-吡喃酮。
• Catalytic Asymmetric [3+2] Annulation of Allylsilanes with Isatins: Synthesis of Spirooxindoles
  作者：Nadine V. Hanhan、Nicolas R. Ball-Jones、Ngon T. Tran、Annaliese K. Franz

  DOI：10.1002/anie.201105739

  日期：2012.1.23

  Silyl‐inspired spirocycle: The title reaction is the first example of a catalytic asymmetric [3+2] annulation reaction with allylsilanes. The annulation reaction utilizes a chiral ScCl2(SbF6)/L catalyst and TMSCl as a promoter to afford spirooxindoles in excellent enantioselectivity at room temperature. The SiC bond can be oxidized to deliver hydroxy‐substituted spirooxindoles. TMS=trimethylsilyl

  Silyl-inspired spirocycle：标题反应是与烯丙基硅烷催化不对称 [3+2]环化反应的第一个例子。环化反应利用手性 ScCl 2 (SbF 6 )/L 催化剂和 TMSCl 作为促进剂，在室温下以优异的对映选择性提供螺环吲哚。所述Si  C键的可被氧化以提供羟基取代spirooxindoles。TMS=三甲基甲硅烷基。
• Synthesis of Spirocarbamate Oxindoles via Intramolecular Trapping of a β-Silyl Carbocation by an <i>N</i>-Boc Group
  作者：Benjamin H. Shupe、Emily E. Allen、Jacob P. MacDonald、Sean O. Wilson、Annaliese K. Franz

  DOI：10.1021/ol4010867

  日期：2013.7.5

  We report the Lewis acid catalyzed additions of allylsilanes to N-Boc-iminooxindoles and the formation of novel silicon-containing spirocarbamates via intramolecular trapping of a β-silyl carbocation by an N-Boc group. Several transformations display the synthetic utility of these spirocarbamate oxindoles, including a reductive cyclization to access new silylated furoindoline derivatives.

  我们报告烯丙基硅烷的路易斯酸催化增补Ñ -Boc-iminooxindoles和新的含硅的spirocarbamates经由β -甲硅烷基碳阳离子的分子内俘获由形成Ñ -Boc基团。一些转化显示了这些螺氨基甲酸酯羟吲哚的合成效用，包括还原环化以获取新的甲硅烷基化呋喃二氢吲哚衍生物。