(2RS,3SR)-1-methylene-2,3-dipropylcyclopropane

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: (2RS,3SR)-1-methylene-2,3-dipropylcyclopropane
• 英文别名: Pr2C3H2CH2；(2R,3S)-1-methylidene-2,3-dipropylcyclopropane
• 化学式: C₁₀H₁₈
• 分子量: 138.253
• InChiKey: WBXMNQXEVVNNBP-AOOOYVTPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 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：

  (2RS,3SR)-1-methylene-2,3-dipropylcyclopropane 、 2-(methyldiphenylsilyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 在 Pd₂(C₆H₅CHCHCOCHCHC₆H₅)3 、 (P)-H(C₁₀H₆N₂(C₅H₁₁O)2)950(C₁₅H₉N₂P(C₈H₉)2)50C₇H₇ 作用下， 以 甲苯 为溶剂， 以86%的产率得到(4S,5S)-4-(methyldiphenylsilyl)-5-[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethenyl]octane
  参考文献：
  名称：

  Enhanced Catalyst Activity and Enantioselectivity with Chirality-Switchable Polymer Ligand PQXphos in Pd-Catalyzed Asymmetric Silaborative Cleavage of meso-Methylenecyclopropanes

  摘要：

  The poly(quinoxaline-2,3-diyl)-based helically chiral phosphine ligands PQXphos exhibited high enantioselectivities up to 97% ee in palladium-catalyzed desymmetrization of meso-1,2-dialkylsubstituted-3-methylenecyclopropanes through silaborative cleavage of the C C bond. The observed enantioselectivities were higher than those obtained with 2-diarylphosphino-1,1'-binaphthyl in our original report. Remarkable rate enhancement was also observed with a series of PQXphos in comparison with the corresponding low-molecular weight ligands.

  DOI：

  10.1021/ja303506k
• 作为产物：
  描述：

  在 potassium tert-butylate 作用下， 以 二甲基亚砜 为溶剂， 生成 (2RS,3SR)-1-methylene-2,3-dipropylcyclopropane 、 (2SR,3SR)-1-methylene-2,3-dipropylcyclopropane
  参考文献：
  名称：

  亚甲基环丙烷的镍催化开环加氢酰化：由醛合成 γ,δ-不饱和酮

  摘要：

  已开发出镍催化的亚甲基环丙烷 (MCP) 的分子间加氢酰化。该反应通过环丙烷环的近端 CC 键的立体有择裂解进行，得到具有高非对映选择性的 γ,δ-不饱和酮。由 Ni(cod)(2) 和 P(n-Bu)(3) 以 1:1 的 P/Ni 比原位生成的镍催化剂对氢化酰化有效，其中苯甲醛衍生物、杂芳基醛和脂肪族醛与 MCP 在 60-100 摄氏度下反应，以高产率提供相应的酮。

  DOI：

  10.1021/ja9046894

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。
• Palladium-Catalyzed Asymmetric Silaborative C−C Cleavage of <i>meso</i>-Methylenecyclopropanes
  作者：Toshimichi Ohmura、Hiroki Taniguchi、Yoshiyuki Kondo、Michinori Suginome

  DOI：10.1021/ja0703170

  日期：2007.3.1

  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.
• Nickel-Catalyzed Ring-Opening Hydroacylation of Methylenecyclopropanes: Synthesis of γ,δ-Unsaturated Ketones from Aldehydes
  作者：Hiroki Taniguchi、Toshimichi Ohmura、Michinori Suginome

  DOI：10.1021/ja9046894

  日期：2009.8.19

  ring to give gamma,delta-unsaturated ketones with high diastereoselectivities. A nickel catalyst generated in situ from Ni(cod)(2) and P(n-Bu)(3) with a P/Ni ratio of 1:1 is effective for the hydroacylation, in which benzaldehyde derivatives, heteroaryl aldehydes, and aliphatic aldehydes react with MCPs at 60-100 degrees C to afford the corresponding ketones in high yields.

  已开发出镍催化的亚甲基环丙烷 (MCP) 的分子间加氢酰化。该反应通过环丙烷环的近端 CC 键的立体有择裂解进行，得到具有高非对映选择性的 γ,δ-不饱和酮。由 Ni(cod)(2) 和 P(n-Bu)(3) 以 1:1 的 P/Ni 比原位生成的镍催化剂对氢化酰化有效，其中苯甲醛衍生物、杂芳基醛和脂肪族醛与 MCP 在 60-100 摄氏度下反应，以高产率提供相应的酮。