<(3-ethenyl-1-cyclohexen-1-yl)oxy>trimethylsilane | 78828-42-9

• 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: <(3-ethenyl-1-cyclohexen-1-yl)oxy>trimethylsilane
• 英文别名: trimethyl((3-vinylcyclohex-1-en-1-yl)oxy)silane；trimethyl-(3-vinylcyclohex-1-enyloxy)silane；3-ethenyl-1-(trimethylsiloxy)cyclohexene；cyclohexenyloxytrimethylsilane；[(3-ethenyl-1-cyclohexen-1-yl)oxy]trimethylsilane；Cyclohexene, 1-(trimethylsilyloxy)-3-vinyl-；(3-ethenylcyclohexen-1-yl)oxy-trimethylsilane
• CAS: 78828-42-9
• 化学式: C₁₁H₂₀OSi
• 分子量: 196.365
• InChiKey: JONSWFIAIKAFRI-UHFFFAOYSA-N

物化性质

• 沸点：
  88-89 °C(Press: 23 Torr)
• 密度：
  0.88±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.71
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  <(3-ethenyl-1-cyclohexen-1-yl)oxy>trimethylsilane 在 tris(dibenzoylmethano)iron(III) 盐酸 、 samarium diiodide 、 氢溴酸 、 sodium iodide 作用下， 以 四氢呋喃 、 正己烷 、 丙酮 为溶剂， 反应 14.0h， 生成 Bicyclo<3.2.1>octan-1-ol
  参考文献：
  名称：

  A facile synthesis of bicyclo[m.n.1]alkan-1-ols. Evidence for organosamarium intermediates in the samarium(II) iodide promoted intramolecular Barbier-type reaction

  摘要：

  Samarium(II) iodide (SmI2) has been successfully employed as a reductive coupling agent for the intramolecular Barbier-type synthesis of bicyclo[m.n.1]alkan-1-ols. Thus, a variety of 3-(omega-iodoalkyl)cycloalkanones, upon treatment with SmI2 and a catalytic quantity of iron complex in tetrahydrofuran (THF), provide the title compounds in excellent yields. The reaction is quite general for the construction of diverse bicyclic ring systems, including the highly strained bicyclo[2.1.1]hexan-1-ol. In addition to exploring the synthetic utility of this reaction, studies have been performed which provide insight on the mechanistic details of the SmI2-promoted intramolecular Barbier-type synthesis. Compelling evidence for the intermediacy of organosamarium species has thus been gathered.

  DOI：

  10.1021/jo00013a008
• 作为产物：
  描述：

  三甲基氯硅烷 、 在 六甲基磷酰三胺 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 生成 <(3-ethenyl-1-cyclohexen-1-yl)oxy>trimethylsilane
  参考文献：
  名称：

  Total syntheses of the proposed structures of cuevaene A

  摘要：

  Two proposed structures of cuevaene A were synthesized and the NMR spectra of both structures are proved to be inconsistent with those of the natural product. The structure of cuevaene A is still unclear and needs to be revised. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2010.06.133

文献信息

• The Kharasch reaction revisited: CuX3Li2-catalyzed conjugate addition reactions of Grignard reagents
  作者：Manfred T. Reetz、Alois Kindler

  DOI：10.1016/0022-328x(95)05699-p

  日期：1995.10

  The conjugate addition of Grignard reagents RMgX to α,β-unsaturated ketones and esters is effectively catalyzed by soluble copper ate-complexes of the type CuX3Li2, e.g. CuI · 2LiCl. In the presence of Me3SiCl the corresponding ketone enolsilanes are formed in high yield and selectivity. Diasteroselectivity in the case of chiral ketones is similar to that observed by using stoichiometric amounts of

  格氏试剂RMgX向α，β-不饱和酮和酯的共轭加成可通过CuX 3 Li 2类型的可溶性铜酸酯络合物（例如CuI·2LiCl ）有效地催化。在Me 3 SiCl存在下，可以高产率和高选择性形成相应的酮烯醇硅烷。在手性酮的情况下，非对映选择性类似于通过使用化学计量的铜酸盐R 2 CuLi所观察到的非对映选择性。因此，CuX 3 Li 2催化的格氏试剂的1，4-加成可能是工业上可行的方法。
• A Strategy toward Icetexane Natural Products
  作者：Daniel J. Moon、Mohammad Al‐Amin、Robert S. Lewis、Kimberly M. Arnold、Glenn P. A. Yap、Jennifer Sims‐Mourtada、William J. Chain

  DOI：10.1002/ejoc.201800707

  日期：2018.7.6

  Icetexane diterpenoids are richly complex polycyclic natural products that have been described with a variety of biological activities. We report here a general synthetic approach toward the 6-7-6 tricyclic core structure of these interesting synthetic targets based on a two-step enolate alkylation and ring-closing metathesis reaction sequence.

  Icetexane 二萜是丰富复杂的多环天然产物，已被描述为具有多种生物活性。我们在此报告了一种基于两步烯醇化物烷基化和闭环复分解反应序列的针对这些有趣合成目标的 6-7-6 三环核心结构的一般合成方法。
• New method for preparing βγ-unsaturated ketones: use of phenylselenoacetaldehyde
  作者：Derrick L. J. Clive、Charles G. Russell

  DOI：10.1039/c39810000434

  日期：——

  Zinc enolates derived from ketones condense efficiently with phenylselenoacetaldehyde and the products are converted into βγ-unsaturated kmmetones by the action of methanesulphonyl chloride and triethylamine.

  由酮衍生的烯醇化物的锌与phenylselenoacetaldehyde有效地冷凝和产品转换成βγ由甲磺酰氯和三乙胺的动作不饱和kmmetones。
• Rules for ring-fusion geometry and the preparation of trans- or cis-fused bicyclic compounds by radical closure
  作者：Derrick L. J. Clive、David R. Cheshire、Lu Set

  DOI：10.1039/c39870000353

  日期：——

  Aldol condensation with (phenylseleno)acetaldehyde and radical cyclization leads to cis-fused bicyclic compounds when applied (Scheme 1) to esters of cycloalk-2-enylacetic acid; trans-isomers are formed when the reactions are used (Scheme 2) in conjunction with organocuprate-mediated addition to cycloalkenones.

  当将醛醇与（苯基硒基）乙醛缩合并进行自由基环化时，将其应用于环烷-2-烯基乙酸的酯时（方案1），会形成顺式稠合的双环化合物。当使用反应（方案2）与有机铜酸酯介导的向环烯酮的加成结合时，形成反式异构体。
• A practical method for regiocontrolled one-carbon ring contraction
  作者：Matthew J. Mitcheltree、Zef A. Konst、Seth B. Herzon

  DOI：10.1016/j.tet.2013.04.027

  日期：2013.7

  A practical and efficient method for the perfluorobutanesulfonyl azide-mediated one-carbon ring contraction of cyclic enoxysilanes is described. High-yielding procedures for the elaboration of the resulting N-acyl sulfonamide products are reported.

  描述了一种实用且有效的方法，用于全氟丁烷磺酰叠氮化物介导的环状环氧硅烷的一碳环收缩。报道了详细的高产程序，用于制备所得的N-酰基磺酰胺产物。