ο-methylenebicyclo<5.1.0>octane | 54211-15-3

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: ο-methylenebicyclo<5.1.0>octane
• 英文别名: cis-8-methylenebicyclo<5.1.0>octane；cis-8-methylenebicyclo(5.1.0)octan；8-methylenebicyclo[5.1.0]octane；8-Methylenbicyclo<5.1.0>octan；(1R,7S)-8-methylidenebicyclo[5.1.0]octane
• CAS: 54211-15-3；115411-11-5
• 化学式: C₉H₁₄
• 分子量: 122.21
• InChiKey: MUDRFXBMCDULFP-DTORHVGOSA-N

物化性质

• 沸点：
  99-100 °C(Press: 9 Torr)
• 密度：
  0.89±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

安全信息

• 海关编码：
  2902199090

反应信息

• 作为反应物：
  描述：

  ο-methylenebicyclo<5.1.0>octane 在 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 48.0h， 生成
  参考文献：
  名称：

  Palladium-Catalyzed Asymmetric Silaborative C−C Cleavage of meso-Methylenecyclopropanes

  摘要：

  An enantioselective silaborative C-C cleavage of meso-methylenecyclopropanes (meso-MCPs) was achieved by using a palladium catalyst bearing a chiral monodentate phosphine ligand. The (R)-2-bis(3,5-dimethylphenyl)phosphino-1,1'-binaphthyl gave the highest enantioselectivity in the reactions with (methyldiphenylsilyl)pinacolborane at 50 degrees C, affording derivatives of 2-boryl-4-silyl-1-butene in high yields with high enantiomeric excesses. The reactions of bicyclic MCPs that have fused five- to eight-membered rings gave the corresponding products with 89-91% ee, whereas a little lower ee was observed in the reaction of a non-fused MCP (81% ee). Synthetic applications of the products were demonstrated through synthesis of beta-silyl ketones by H2O2 oxidation and synthesis of stereodefined homoallylic alcohols via homologation-allylboration sequence, in which the chiral beta-substituent of the allylborane has critical impact on the diastereochemical outcome.

  DOI：

  10.1021/ja0703170
• 作为产物：
  描述：

  8,8-dibromobicyclo[5.1.0]octane 、 碘甲烷 生成 ο-methylenebicyclo<5.1.0>octane
  参考文献：
  名称：

  Copper(I) catalysis of olefin photoreactions. Photorearrangement and photofragmentation of methylenecyclopropanes

  摘要：

  DOI：

  10.1021/ja00470a027

文献信息

• Nickel-Catalyzed Regio- and Stereoselective Reductive Coupling between Methylenecyclopropanes, Aldehydes, and Triethylborane with Retention of the Cyclopropane Ring
  作者：Kenichi Ogata、Daisuke Shimada、Shin-ichi Fukuzawa

  DOI：10.1002/chem.201200271

  日期：2012.5.14

  Running rings: The first regio‐ and stereoselective reductive coupling between methylenecyclopropanes, aldehydes, and triethylborane with retention of the cyclopropane ring was achieved using a nickel–phosphine catalyst (see scheme). The reductive coupling reaction constructed a stereo‐defined cyclopropane ring with formation of a quaternary stereogenic carbon center.

  运转环：使用镍-膦催化剂（见方案）在亚甲基环丙烷，醛和三乙基硼烷之间保留环丙烷环的第一区域和立体选择性还原偶联。还原偶联反应构建了一个立体定义的环丙烷环，并形成了一个四级立体原子碳中心。
• Synthesis of <i>trans</i>-Cycloalkenes via Enantioselective Cyclopropanation and Skeletal Rearrangement
  作者：Tomoya Miura、Takayuki Nakamuro、Chia-Jung Liang、Masahiro Murakami

  DOI：10.1021/ja5096045

  日期：2014.11.12

  An efficient one-pot two-step procedure for asymmetric synthesis of piperidine-fused trans-cycloalkenes is reported. The method comprises the initial enantioselective installation of another cyclopropane ring onto methylenecyclopropanes and the subsequent thermal skeletal rearrangement in which the installed and inherent cyclopropane rings are both opened. A concerted mechanism is proposed for the

  报道了一种用于不对称合成哌啶稠合的反式环烯烃的高效一锅两步法。该方法包括在亚甲基环丙烷上的初始对映选择性安装另一个环丙烷环和随后的热骨架重排，其中安装的环丙烷环和固有的环丙烷环都打开。为后者的热重排反应提出了协同机制以及封闭的过渡态模型。
• Nickel-Catalyzed Ring-Opening Alkylative Coupling of Enone with Methylenecyclopropane in the Presence of Triethylborane
  作者：Kenichi Ogata、Daisuke Shimada、Shouichi Furuya、Shin-ichi Fukuzawa

  DOI：10.1021/ol303548x

  日期：2013.3.15

  Nickel-catalyzed alkylative coupling of an enone or enal with methylenecyclopropane in the presence of triethylborane was achieved via stereospecific proximal C–C bond cleavage of methylenecyclopropane. With the use of methylenecyclopropane possessing an acyclic alkyl substituent, this reaction was also accompanied by the β-hydrogen elimination.

  在三乙基硼烷存在下，烯酮或烯醛与亚甲基环丙烷的镍催化烷基化偶联是通过亚甲基环丙烷的立体定向近端C-C键裂解实现的。通过使用具有无环烷基取代基的亚甲基环丙烷，该反应还伴随有β-氢的消除。
• Platinum(0)-Catalyzed Diboration of Methylenecyclopropanes with Bis(pinacolato)diboron: A Selective Route to 2,4-Bis(boryl)-1-butenes
  作者：Tatsuo Ishiyama、Seiji Momota、Norio Miyaura

  DOI：10.1055/s-1999-2957

  日期：1999.11

  Title Platinum(0)-Catalyzed Diboration of Methylenecyclopropanes with Bis(pinacolato)diboron: A Selective Route to 2,4Bis(boryl)-1-butenes Author(s) Ishiyama, Tatsuo; Momota, Seiji; Miyaura, Norio Citation Synlett, 1999(11), 1790-1792 https://doi.org/10.1055/s-1999-2957 Issue Date 1999-11 Doc URL http://hdl.handle.net/2115/56161 Type article (author version) File Information (19) B-B + △= (Com).pdf

  标题 Platinum(0)-Catalyzed Diboration of Methylenecyclopropanes with Bis(pinacolato)diboron: A Selective Route to 2,4 Bis(boryl)-1-butenes 桃田诚二；Miyaura, Norio Citation Synlett, 1999(11), 1790-1792 https://doi.org/10.1055/s-1999-2957 发行日期 1999-11 Doc URL http://hdl.handle.net/2115/56161 类型文章（作者版）文件信息（19）BB+△=（com）.pdf
• Shirakura, Masamichi; Suginome, Michinori, Journal of the American Chemical Society, 2009, vol. 131, p. 5060 - 5061
  作者：Shirakura, Masamichi、Suginome, Michinori

  DOI：——

  日期：——