1-(1-Cyclopropylideneethyl)-3-methoxybenzene | 244065-15-4

• 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: 1-(1-Cyclopropylideneethyl)-3-methoxybenzene
• CAS: 244065-15-4
• 化学式: C₁₂H₁₄O
• 分子量: 174.243
• InChiKey: XEYZAUZYHGIRFX-UHFFFAOYSA-N

物化性质

• 沸点：
  276.2±9.0 °C(Predicted)
• 密度：
  1.056±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 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-Cyclopropylideneethyl)-3-methoxybenzene 在 咪唑 、 sodium tetrahydroborate 、 cerium(III) chloride 、 氨 、 mercury(II) trifluoroacetate 、 sodium 、 碳酸氢钠 、 间氯过氧苯甲酸 作用下， 以 甲醇 、 乙醇 为溶剂， 反应 9.0h， 生成
  参考文献：
  名称：

  Total Synthesis of (±)-Scirpene

  摘要：

  The racemate of scirpene, 12,13-epoxytrichothec-9-ene, was synthesized from 3-methoxyacetophenone. The key step in the synthesis is the palladium-mediated ring expansion reaction of the vinylcyclobutanol derivative, prepared via the oxidative ring expansion reaction of the cyclopropylidene, (3S*)-3-[(1S*,6S*)-3-Methyl-9-oxabicyclo[4.3.0]non-2-en-6-yl]-3-methyl-2 methylenecyclo-pentan-1-one formed from the reaction was converted into (+/-)-scirpene through the ring opening of tetrahydrofuran part, followed by cyclization for construction of the desired skeleton.

  DOI：

  10.1021/ol9901164
• 作为产物：
  描述：

  溴化环丙基三苯鏻 、 3-甲氧基苯乙酮 在 sodium hydride 作用下， 以92%的产率得到1-(1-Cyclopropylideneethyl)-3-methoxybenzene
  参考文献：
  名称：

  Total Synthesis of (±)-Scirpene

  摘要：

  The racemate of scirpene, 12,13-epoxytrichothec-9-ene, was synthesized from 3-methoxyacetophenone. The key step in the synthesis is the palladium-mediated ring expansion reaction of the vinylcyclobutanol derivative, prepared via the oxidative ring expansion reaction of the cyclopropylidene, (3S*)-3-[(1S*,6S*)-3-Methyl-9-oxabicyclo[4.3.0]non-2-en-6-yl]-3-methyl-2 methylenecyclo-pentan-1-one formed from the reaction was converted into (+/-)-scirpene through the ring opening of tetrahydrofuran part, followed by cyclization for construction of the desired skeleton.

  DOI：

  10.1021/ol9901164

文献信息

• Highly Enantioselective Nickel-Catalyzed Hydrocyanation of Disubstituted Methylenecyclopropanes Enabled by TADDOL-based Diphosphite Ligands
  作者：Rongrong Yu、Xianjie Fang

  DOI：10.1021/acs.orglett.9b04374

  日期：2020.1.17

  A vast range of novel TADDOL-based diphosphite ligands were first synthesized and applied in the nickel-catalyzed asymmetric hydrocyanation of disubstituted methylenecyclopropanes. By employing these new catalysts, the conversion of diverse methylenecyclopropanes into their corresponding allylic nitriles was first enabled, in good yield with excellent enantioselectivities.

  首先合成了大量新颖的基于TADDOL的二亚磷酸酯配体，并将其应用于镍催化的二取代的亚甲基环丙烷的不对称氢氰化反应中。通过使用这些新的催化剂，首先能够以良好的产率和优异的对映选择性将多种亚甲基环丙烷转化为其相应的烯丙基腈。
• Enantioselective Synthesis of γ-Aryl-γ-butyrolactones by Sequential Asymmetric Epoxidation, Ring Expansion, and Baeyer−Villiger Oxidation
  作者：Bin Wang、Yu-Mei Shen、Yian Shi

  DOI：10.1021/jo061341j

  日期：2006.12.1

  N-tolyl-substituted oxazolidinone-containing ketone as catalyst and Oxone as oxidant via a sequential asymmetric epoxidation of benzylidenecyclopropanes, ring expansion, and Baeyer−Villiger oxidation. Up to 91% ee was obtained. Optically active cyclobutanones can also be obtained by suppressing the Baeyer−Villiger oxidation with use of more ketone catalyst and less Oxone.

  本文描述了一种γ-丁内酯的对映体选择性合成方法，该方法通过使用亚苄基环丙烷的连续不对称环氧化，扩环和Baeyer-Villiger氧化，使用含N-甲苯基取代的恶唑烷酮的酮为催化剂，以Oxone为氧化剂。获得了高达91％的ee。光学活性的环丁酮也可以通过使用更多的酮催化剂和更少的Oxone抑制Baeyer-Villiger氧化而获得。
• 一种磺酰基取代的α-环丙基苯乙烯类化合物 及其合成方法
  申请人：辽宁石油化工大学

  公开号：CN110483346B

  公开（公告）日：2021-06-18

  本发明公开了一种磺酰基取代的α‑环丙基苯乙烯类化合物及其合成方法，所述合成方法以清洁可持续的可见光为能源，利用亚甲基环丙烷化合物为底物，与苯磺酰氯反应，合成一系列磺酰基取代的α‑环丙基苯乙烯类化合物，该化合物的特点是不仅含有环丙基和苯磺酰基同时还保留了双键结构，操作步骤简单、底物普适性好、具有步骤经济性，使用清洁易得的可见光诱导反应，具有市场经济性以及环境友好等优点。
• Selective Access to Silacyclopentanes and Homoallylsilanes by La-Catalyzed Hydrosilylations of 1-Aryl Methylenecyclopropanes
  作者：Xiaoming Xu、Ailin Gao、Xiufang Xu、Jianfeng Li、Chunming Cui

  DOI：10.1021/jacs.3c12355

  日期：2024.2.14

  their unique reactivity. However, metal-catalyzed hydrosilylation of MCPs has met with very limited successes. In this paper, catalytic selective hydrosilylations of MCPs with some primary silanes using an ene-diamido lanthanum ate complex as the catalyst were described. The catalytic reactions resulted in the selective formation of silacyclopentanes and (E)-homoallylsilanes, respectively, depending on

  亚甲基环丙烷 (MCP) 因其独特的反应性而成为合成化学中的多功能构件。然而，金属催化的 MCP 氢化硅烷化反应取得的成功非常有限。本文描述了使用烯-二酰氨基镧酸酯络合物作为催化剂，MCP 与一些伯硅烷的选择性催化氢化硅烷化反应。根据 MCP 上的取代基，催化反应分别选择性地形成硅杂环戊烷和 ( E )-高烯丙基硅烷。控制和氘化标记实验以及 DFT 计算有力地支持了通过催化级联分子间和分子内氢化硅烷化机制形成硅杂环戊烷。独特的反应活性和选择性可归因于催化剂的大镧离子和ATE结构。
• Total Synthesis of (±)-Scirpene
  作者：Hideo Nemoto、Eiki Takahashi、Masataka Ihara

  DOI：10.1021/ol9901164

  日期：1999.8.1

  The racemate of scirpene, 12,13-epoxytrichothec-9-ene, was synthesized from 3-methoxyacetophenone. The key step in the synthesis is the palladium-mediated ring expansion reaction of the vinylcyclobutanol derivative, prepared via the oxidative ring expansion reaction of the cyclopropylidene, (3S*)-3-[(1S*,6S*)-3-Methyl-9-oxabicyclo[4.3.0]non-2-en-6-yl]-3-methyl-2 methylenecyclo-pentan-1-one formed from the reaction was converted into (+/-)-scirpene through the ring opening of tetrahydrofuran part, followed by cyclization for construction of the desired skeleton.