1-(1-cyclopentenyl)-1-<(tert-butyldimethylsilyl)oxy>ethene | 86891-78-3

• 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: 1-(1-cyclopentenyl)-1-<(tert-butyldimethylsilyl)oxy>ethene
• 英文别名: 1-{[(1,1-dimethylethyl)dimethylsilyloxy]ethenyl}cyclopentene；tert-Butyl{[1-(cyclopent-1-en-1-yl)ethenyl]oxy}dimethylsilane；tert-butyl-[1-(cyclopenten-1-yl)ethenoxy]-dimethylsilane
• CAS: 86891-78-3
• 化学式: C₁₃H₂₄OSi
• 分子量: 224.418
• InChiKey: HARIOQJHHQIUQP-UHFFFAOYSA-N

物化性质

• 沸点：
  253.2±9.0 °C(Predicted)
• 密度：
  0.896±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.63
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.69
• 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：

  1-(1-cyclopentenyl)-1-<(tert-butyldimethylsilyl)oxy>ethene 在 2,6-二甲基吡啶 、 叔丁基二甲硅基三氟甲磺酸酯 、 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 生成 1,2,3,3a,3b,4,9b,10,11,11a-decahydrobenzindeno<5,4-d>pyran-4,11-dione
  参考文献：
  名称：

  Diels-Alder reactions of 2-[(trialkylsilyl)oxy]pyrylium cations of 2H-pyran-2-one and 2H-1-benzopyran-2-one derivatives

  摘要：

  The reactions of 6-methyl-2H-pyran-2-one and 2H-1-benzopyran-2-one with the 2-(trialkylsilyl)oxy dienes 6a-d in the presence of tert-butyldimethylsilyl triflate gave the [4 + 2] cycloadducts 7a-c and 8a-d regio- and stereoselectively in moderate yields. The ring junction in the cycloadducts is cis. The stereochemistry of 8a-d is discussed in terms of the H-1 NMR spectra of the compounds. Similar reactions of 3-(ethoxycarbonyl)-2-pyrones and 3-(alkoxycarbonyl)coumarins with the 2-(trialkylsilyl)oxy dienes 6a-e gave the cycloadducts 14-18 in satisfactory yields. Dehydrogenation of 7c, 8b, and 8c with DDQ in refluxing toluene afforded 23-25, respectively.

  DOI：

  10.1021/jo00017a014
• 作为产物：
  描述：

  1,2-环己二醇 在 manganese(IV) oxide 、 sodium periodate 、 三乙胺 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 水 为溶剂， 反应 6.42h， 生成 1-(1-cyclopentenyl)-1-<(tert-butyldimethylsilyl)oxy>ethene
  参考文献：
  名称：

  顺式环加成取代顺式-Hydrindan-4-ones

  摘要：

  摘要 报道了取代的顺式-hydrandan-4-ones的合成。特别强调季立体位环碳原子的非对映选择性结构。分子间不对称Al（III）促进（4 + 2）-环加成反应是主要的C / C连接工具。探索了进一步构造（4 + 2）-环加成物的机会。 报道了取代的顺式-hydrandan-4-ones的合成。特别强调季立体位环碳原子的非对映选择性结构。分子间不对称Al（III）促进（4 + 2）-环加成反应是主要的C / C连接工具。探索了进一步构造（4 + 2）-环加成物的机会。

  DOI：

  10.1055/s-0034-1378880

文献信息

• Synthesis of the Cyclohepta[<i>e</i>]hydrindane Core of the Marine Homoverrucosane Diterpenoid Gagunin E
  作者：Andreas Schäfer、Martin Hiersemann

  DOI：10.1021/acs.orglett.6b03799

  日期：2017.2.17

  The synthesis of the A–B-cis B–C-trans annulated cyclohepta[e]hydrindane core of gagunin E with a fully elaborated B–C ring segment has been achieved. Using an adaptable A ring building block, the B ring was annulated by (4 + 2)-cycloaddition and the C ring by ring-closing metathesis. The angular methyl groups were attached by electrophilic cyclopropanation–ring opening.

  gagunin E的A–B–顺式B–C-反式环庚七环[ e ]茚满核的合成具有完整的B–C环段。使用可适应的A环结构单元，通过（4 + 2）-环加成法将B环环化，通过闭环复分解将C环环​​化。角甲基通过亲电子环丙烷化环的开环连接。
• Preparation of -butyldimethylsilyl (tbdms) enol ethers using potassium hydride in the presence of tbdms chloride
  作者：John Orban、John V. Turner、Bruce Twitchin

  DOI：10.1016/s0040-4039(01)91129-3

  日期：1984.1

  TBDMS enol ethers can be readily prepared regio- and stereoselectively under equilibrating conditions in high yield by adding potassium hydride to a THF solution of ketone with TBDMS chloride in situ.

  通过在原位用TBDMS氯化物将氢化钾加到酮的THF溶液中，可以在平衡条件下容易地区域选择性和立体选择性地高产率地制备TBDMS烯醇醚。
• Synthetic studies toward the kempane diterpenes. Diels–Alder additions to bicyclic dienes
  作者：Chunjian Liu、Guanglin Bao、D. Jean Burnell

  DOI：10.1039/b104924k

  日期：2001.10.11

  Reduction and then alkylation of a tetracyclic adduct with 1,3-dithienium tetrafluoroborate provided compound 56, which has the correct stereochemistry at three key carbons for elaboration to the kempane diterpenes. Exploratory reactions with tricyclic model compounds and with tetracyclic adducts have been used to assess the development of the desired stereochemistry about the decalin moiety. X-Ray structures

  Diels–Alder的添加 2,6-二甲基-对苯醌以双环二烯24，30和32发生具有非常高的区域选择性，立体和面部选择性。减少 接着 烷基化1,3-二氟四氟硼酸四环加合物制得化合物56，该化合物在三个关键碳原子上具有正确的立体化学，可用于精制the烷二萜。与三环模型化合物和四环加合物的探索性反应已用于评估关于十氢化萘部分的所需立体化学的发展。用于X射线结构52，53和59进行了测定。
• Preparation of optically active photopyridone by lipase-catalysed asymmetric resolution 1
  作者：Hiroshi Hongo、Kazuto Iwasa、Chizuko Kabuto、Hisao Matsuzaki、Hiroto Nakano

  DOI：10.1039/a605698i

  日期：——

  Optically active photopyridones possessing synthetic versatility are obtained conveniently by lipase-catalysed enantioselective acylation or hydrolysis of racemic photopyridones, and the absolute configurations are determined by chemical correlation, X-ray crystallographic and CD spectral analyses.

  通过脂肪酶催化外消旋光吡啶酮的对映体选择性酰化或水解，可方便地获得具有合成多功能性的光学活性光吡啶酮，并通过化学相关性、X 射线晶体学和 CD 光谱分析确定其绝对构型。
• Synthesis of cyclopentanthraquinones: analogs of mitomycin C
  作者：Bernd Kohler、Tsann Long Su、Ting Chao Chou、Xiang Jun Jiang、Kyoichi A. Watanabe

  DOI：10.1021/jo00059a014

  日期：1993.3

  2,3-Dihydro-1H-cyclopent[a]anthracene-6,11-dione (cyclopentanthraquinone) derivatives bearing a mustard side chain at C-4 and an aziridine ring at the cyclopentene moiety were synthesized. Such a compound may be viewed as an analogue of mitomycin C (MC) and may exhibit bifunctional DNA-alkylating and DNA-intercalating agent. The key intermediate, 4-hydroxy-2,3-di-O-substituted cyclopentanthraquinone, was synthesized by Deils-Alder reaction of naphthoquinone with various 4,5-dihydroxy-1-vinylcyclopent-1-ene derivatives. Introduction of a mustard side chain to the OH group at C-4 and subsequent construction of an aziridine-ring on C2-C3 of the cyclopentanthraquinone molecule furnished the target compound, 2,3-aziridino-4-[2-[NN-bis(2-chloroethyl)amino]ethoxy]-2,3-dihydro-1H-cyclopent [a] anthracene-6,11-dione (37). It was found that both the aziridine function and the mustard side chain play a significant role in their cytotoxicity against leukemic L1210 and HL-60 cell growth in culture and the inhibition of topoisomerase II kDNA decatenation.