2-naphthyl-1-methylenecyclopropane

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2-naphthyl-1-methylenecyclopropane
• 英文别名: 2-(2-Methylidenecyclopropyl)naphthalene
• 化学式: C₁₄H₁₂
• 分子量: 180.249
• InChiKey: BPHYKJPUGPEDME-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 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：

  1,3-二氢-2-苯并噻吩-1,3-二酮 、 2-naphthyl-1-methylenecyclopropane 在 bis(1,5-cyclooctadiene)nickel (0) 、 甲铝双(2,6-二叔丁基-4-苯甲醚) 、 二甲基苯基磷 作用下， 以 甲苯 为溶剂， 130.0 ℃ 、101.33 kPa 条件下， 反应 9.0h， 以82%的产率得到(E)-3-methyl-3-(2-(naphthalen-2-yl)vinyl)benzo[c]thiophen-1(3H)-one
  参考文献：
  名称：

  亚甲基环丙烷作为C1合成单元：通过镍催化剂进行[1 + 4]环加成。

  摘要：

  镍催化的亚甲基环丙烷与硫代酸酐的反应可通过[1 + 4]环加成反应生成含硫的杂环化合物。该反应代表了亚甲基环丙烷的一种新用途，它可以取代一氧化碳，异氰酸酯和费歇尔卡宾络合物，成为可能的一碳结构单元。

  DOI：

  10.1039/c1cc13540f
• 作为产物：
  描述：

  2-(2-甲基-2-丙烯-1-基)萘 在 正丁基锂 、 四甲基乙二胺 、 1,2-二溴乙烷 作用下， 以 正己烷 为溶剂， 反应 16.0h， 生成 2-naphthyl-1-methylenecyclopropane
  参考文献：
  名称：

  Reactions of the Lithium Salts of the Tribenzylidenemethane Dianion, Diphenylacetone Dianion, and Related Compounds

  摘要：

  Potentially synthetically useful reactions of the dilithium salts of the title dianions have been investigated, Electrophilic quenching with a variety of reagents usually leads to the expected products in good yield. Quenching the diphenylacetone dianion with 1 equiv of trimethylchlorosilane, however, gives a good yield of 1,3-diphenylallene obtained by formal elimination of a trimethylsiloxy anion from an intermediate monoquenched monoanion salt. NMR studies, however, do not reveal the intermediacy of the 1,3-diphenyl-2-(trimethylsiloxy)allyl anion but rather suggest that the initial reaction site is at carbon, rather than oxygen, Oxidation of the dianions leads either to ring closure or dimerization for the tribenzylidenemethane dianion and to dimerization for the diphenylacetone dianion. The dimerization reactions are stereospecific, both with respect to the two new stereocenters produced and for the double bonds of the bis-silyl enol ether products if the dimeric bis-enolate dianion products are quenched with trimethylchlorosilane.

  DOI：

  10.1021/jo971113c

文献信息

• Iron-Catalyzed Ortho C–H Homoallylation of Aromatic Ketones with Methylenecyclopropanes
  作者：Naoki Kimura、Shiori Katta、Yoichi Kitazawa、Takuya Kochi、Fumitoshi Kakiuchi

  DOI：10.1021/jacs.1c00237

  日期：2021.3.31

  We report here a C–H homoallylation reaction of aromatic ketones with methylenecyclopropanes (MCPs) only using a catalytic amount of Fe(PMe3)4. A variety of aromatic ketones and MCPs are applicable to the reaction to form ortho-homoallylated aromatic ketones selectively via regioselective scission of the three-membered rings. The homoallylated products are amenable to further elaborations, providing

  我们在这里报告仅使用催化量的Fe（PMe 3）4与芳族酮与亚甲基环丙烷（MCPs）进行C–H均化反应。多种芳族酮和MCP可用于通过三元环的区域选择性断裂选择性地形成邻均芳基化的芳族酮的反应。均化的产物适合于进一步的修饰，从而提供官能化的1，2-二氢萘。
• Nickel-Catalyzed Regioselective Carbomagnesation of Methylenecyclopropanes through a Site-Selective Carbon-Carbon Bond Cleavage
  作者：Jun Terao、Masahiro Tomita、Surya Prakash Singh、Nobuaki Kambe

  DOI：10.1002/anie.200904721

  日期：2010.1.4

  Unwringing the ring: Methylenecyclopropanes reacted with vinyl and aryl Grignard reagents in the presence of a nickel catalyst to afford vinyl‐ and arylmagnesation products, respectively, through a selective CC bond cleavage (see scheme). The reaction provides a new method for the preparation of substituted homoallyl and allyl Grignard reagents.

  解开环：亚甲基环丙烷在镍催化剂存在下与乙烯基和芳基格氏试剂反应，通过选择性的CC键裂解分别得到乙烯基和芳基磁化产物（参见方案）。该反应提供了一种制备取代的烯丙基和烯丙基格氏试剂的新方法。
• Highly Stereoselective Synthesis of (Borylmethyl)cyclopropylamines by Copper-Catalyzed Aminoboration of Methylenecyclopropanes
  作者：Ryosuke Sakae、Naoki Matsuda、Koji Hirano、Tetsuya Satoh、Masahiro Miura

  DOI：10.1021/ol5001507

  日期：2014.2.21

  A Cu-catalyzed aminoboration of 1-methylenecyclopropanes with bis(pinacolato)diboron and O-benzoyl-N,N-dialkylhydroxylamines has been developed. The Cu catalysis provides a rapid and concise access to (borylmethyl)cyclopropylamines in a highly regio- and diastereoselective manner. The products obtained can be useful building blocks for the synthesis of potential antidepressants, trans-2-arylcyclopropylamine

  已经开发了具有双（频哪醇）二硼和O-苯甲酰基-N，N-二烷基羟胺的Cu催化的1-亚甲基环丙烷的氨基硼化。铜催化作用以高度区域选择性和非对映选择性的方式提供了快速，简捷的（硼烷基甲基）环丙胺的途径。获得的产物可能是合成潜在的抗抑郁药反式-2-芳基环丙胺衍生物的有用组成部分。
• Copper-Catalyzed Regioselective Ring-Opening Hydroamination of Methylenecyclopropanes
  作者：Daiki Nishikawa、Ryosuke Sakae、Yuya Miki、Koji Hirano、Masahiro Miura

  DOI：10.1021/acs.joc.6b02483

  日期：2016.12.16

  A copper-catalyzed ring-opening hydroamination of methylenecyclopropanes with polymethylhydrosiloxane and O-benzoylhydroxylamines has been developed. The cyclopropane C–C bond cleavage occurs selectively at the more congested proximal position, and the corresponding homoallylamines are obtained in good to excellent yields. The umpolung electrophilic amination strategy with the hydroxylamine derivatives

  已经开发了亚甲基环丙烷与聚甲基氢硅氧烷和O-苯甲酰基羟胺的铜催化的开环加氢胺化。环丙烷的C–C键断裂选择性地发生在更拥挤的近端位置，并且相应的高烯丙基胺以良好或极好的收率获得。羟胺衍生物的聚苯胺亲电胺化策略可以为亚甲基环丙烷在催化加氢胺化反应中提供新的反应方式。
• Reactions of the Lithium Salts of the Tribenzylidenemethane Dianion, Diphenylacetone Dianion, and Related Compounds
  作者：Ortrun Witt、Harald Mauser、Thomas Friedl、Dieter Wilhelm、Timothy Clark

  DOI：10.1021/jo971113c

  日期：1998.2.1

  Potentially synthetically useful reactions of the dilithium salts of the title dianions have been investigated, Electrophilic quenching with a variety of reagents usually leads to the expected products in good yield. Quenching the diphenylacetone dianion with 1 equiv of trimethylchlorosilane, however, gives a good yield of 1,3-diphenylallene obtained by formal elimination of a trimethylsiloxy anion from an intermediate monoquenched monoanion salt. NMR studies, however, do not reveal the intermediacy of the 1,3-diphenyl-2-(trimethylsiloxy)allyl anion but rather suggest that the initial reaction site is at carbon, rather than oxygen, Oxidation of the dianions leads either to ring closure or dimerization for the tribenzylidenemethane dianion and to dimerization for the diphenylacetone dianion. The dimerization reactions are stereospecific, both with respect to the two new stereocenters produced and for the double bonds of the bis-silyl enol ether products if the dimeric bis-enolate dianion products are quenched with trimethylchlorosilane.