trans-1-butyl-2-phenylcyclopropane | 33450-83-8

• 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: trans-1-butyl-2-phenylcyclopropane
• 英文别名: [(1S,2S)-2-butylcyclopropyl]benzene
• CAS: 33450-83-8
• 化学式: C₁₃H₁₈
• 分子量: 174.286
• InChiKey: HJHWOPNCJJJNDB-QWHCGFSZSA-N

物化性质

• 沸点：
  248.0±7.0 °C(Predicted)
• 密度：
  0.926±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  (2,2-二溴环丙基)苯 在 正丁基锂 、 1,1,2-三氯三氟乙烷（CFC-113） 、 zinc(II) chloride 作用下， 反应 1.0h， 生成 trans-1-butyl-2-phenylcyclopropane
  参考文献：
  名称：

  Stereoselective carbon-carbon bond-forming reaction of 1,1-dibromocyclopropanes via 1-halocyclopropylzincates

  摘要：

  Lithium trialkylzincates react efficiently with 1,1-dibromocyclopropanes 5 to give the corresponding alkylation products 7 nonstereoselectively. The reaction proceeds through a 1,2-alkyl migration of the intermediately formed zincate carbenoid 3 in an invertive manner. Reaction of 5 with BuLi followed by successive treatment of the resulting trans-lithium carbenoid 8 with ZnCl2 and an alkyllithium (R2Li) produces the zincate carbenoid trans-3, which, in turn, gives cis-7 stereoselectively (Method B). Reaction of lithium trialkylzincates and trans-1-bromo-1-chlorocyclopropanes 11 prepared in situ by chlorination of the trans-lithium carbenoid with CF2ClCFCl2 yields trans-7 stereoselectively (Method C). 1-Alkylcyclopropylzinc 4, an intermediate of the alkylation reaction, reacts smoothly with acyl, aryl, and alkenyl halides in the presence of a palladium(0) catalyst to give the corresponding coupling products 15 and 16. By generating the cyclopropylzinc intermediate 4 stereoselectively by using method B or C, one can obtain the desired stereoisomers of the coupling products with high selectivity.

  DOI：

  10.1021/jo00063a010

文献信息

• Stereoselective One-pot Dialkylation of<i>gem</i>-Dihalocyclopropanes by Means of Dialkylcopperlithiums
  作者：Katuzi Kitatani、Tamejiro Hiyama、Hitosi Nozaki

  DOI：10.1246/bcsj.50.1600

  日期：1977.6

  (2 and 3) is established by successive treatment with dibutylcopperlithium and several electrophiles. This sequence is found to be stereochemically controllable and is successfully applied to dl-sirenin synthesis. In contrast to the reaction of dibutylcopperlithium, dimethyl- and divinylcopperlithiums convert 1,1-dibromo-2-phenylcyclopropane (1a) into 1-bromo-1-methyl- and 1-bromo-1-vinyl-2-phenylcyclopropanes

  通过用二丁基锂锂和几种亲电子试剂连续处理，可将偕二卤代环丙烷 (1) 转化为 1-烷基-1-丁基环丙烷 (2 和 3)。发现该序列是立体化学可控的，并成功应用于 dl-sirenin 合成。与二丁基铜锂的反应相反，二甲基和二乙烯基铜锂将 1,1-二溴-2-苯基环丙烷 (1a) 转化为 1-溴-1-甲基-和 1-溴-1-乙烯基-2-苯基环丙烷（15a、16a和 15b、16b)。
• Alkylation of Bromocyclopropanes and Bromoarenes by Means of Dibutylcopperlithium and Alkyl Halides
  作者：Tamejiro Hiyama、Hajime Yamamoto、Koji Nishio、Katuzi Kitatani、Hitosi Nozaki

  DOI：10.1246/bcsj.52.3632

  日期：1979.12

  of bromocyclopropanes with excess dibutylcopperlithium in tetrahydrofuran at −48 °C gives the respective organocopper intermediates which upon quenching with excess alkyl halides afford alkylated cyclo-propanes with retention of the configuration. This process is applied to the synthesis of methyl cascarillate. Bromoarenes are also reduced with dibutylcopperlithium and allylarenes are prepared therefrom

  在-48°C 下在四氢呋喃中用过量的二丁基铜锂处理溴环丙烷得到相应的有机铜中间体，当用过量的卤代烷淬灭时，得到保留构型的烷基化环丙烷。该工艺用于合成卡斯卡里酸甲酯。溴芳烃也用二丁基铜锂还原，并由此制备烯丙基芳烃。
• Reaction of gem-Dibromocyclopropanes or Iodobenzofuran with Trialkylmanganate
  作者：Hirotada Kakiya、Rie Inoue、Hiroshi Shinokubo、Koichiro Oshima

  DOI：10.1016/s0040-4020(99)01095-9

  日期：2000.4

  Treatment of gem-dibromocyclopropanes with trialkylmanganate, derived from manganese(II) chloride and three equivalents of Grignard reagent or alkyllithium, followed by an addition of electrophiles provided dialkylated cyclopropanes in good yields. It was found that the reaction of gem-dibromocyclopropanes with alkylmagnesium halide proceeded in the presence of a catalytic amount of manganese(II) chloride

  用衍生自氯化锰（II）和三当量的格氏试剂或烷基锂的锰酸三烷基酯处理宝石-二溴环丙烷，然后加入亲电试剂以良好的收率提供了二烷基化的环丙烷。发现在催化量的氯化锰（II）的存在下，宝石-二溴环丙烷与烷基卤化镁的反应进行。用碘代苯并呋喃代替宝石-二溴环丙烷得到开环产物2-烯基苯酚。
• Palladium-Catalyzed Cross-Coupling Reaction of Cyclopropylboronic Acids with Aryl Triflates
  作者：Min-Liang Yao、Min-Zhi Deng

  DOI：10.1055/s-2000-6313

  日期：——

  In the presence of appropriate base and NaBr, the Suzuki-type reaction of aryl triflates and trans-cyclopropylboronic acids proceed readily to give pure trans-cyclopropylarenes in good to high yields. For the reaction of general aryl triflates, the base KF · 2 H2O is efficient, but in the case of aryl triflates bearing electron donating groups, KF · 2 H2O as a base makes the unexpected phenyl-aryl exchange between the phenyl of Pd(PPh3)4 and the aryl of triflate to occur. The use of K3PO4 · 3 H2O instead of KF · 2 H2O can inhibit the unexpected phenyl-aryl exchange, but the yield of the product is somewhat decreased. The coupling reaction of aryl triflates with the optically active cyclopropylboronic acids, which were easily obtained in good yield and with good to excellent ee (up to 94%) by the asymmetric cyclopropanation of alkenylboronates with optically pure TMTA auxiliary, was also investigated. During the coupling reaction, the absolute configuration of the cyclopropyl group was retained. Thus, a novel method to prepare aryl-substituted cyclopropanes, including highly optically active cyclopropanes, from phenols or arylamines was provided.

  在适当的碱和 NaBr 存在下，芳基三氟酸酯和反式环丙基硼酸的 Suzuki 型反应很容易进行，并以良好至高产率得到纯的反式环丙基烯烃。对于一般的芳基三氟酸酯反应，碱 KF - 2 H2O 是有效的，但对于带有电子捐赠基团的芳基三氟酸酯，KF - 2 H2O 作为碱会使 Pd(PPh3)4 的苯基和三氟酸酯的芳基之间发生意想不到的苯基-芳基交换。使用 K3PO4 - 3 H2O 代替 KF - 2 H2O 可以抑制意想不到的苯基-芳基交换，但生成物的产率会有所下降。通过烯基硼酸酯与光学纯 TMTA 助剂的不对称环丙烷化反应，可以轻松获得收率高、ee 值好到极好（高达 94%）的光学活性环丙基硼酸。在偶联反应过程中，环丙基的绝对构型得以保留。因此，提供了一种从苯酚或芳基胺制备芳基取代环丙烷（包括高光学活性环丙烷）的新方法。
• Dialkylation of gem-dibromocyclopropanes with trialkylmanganate and manganese(II) chloride-catalyzed reaction with alkylmagnesium bromide
  作者：Rie Inoue、Hiroshi Shinokubo、Koichiro Oshima

  DOI：10.1016/0040-4039(96)01082-9

  日期：1996.7

  gem-dibromocyclopropanes with trialkylmanganate, derived from manganese(II) chloride and three equivalents of Grignard reagent or alkyllithium, followed by an addition of electrophiles provided dialkylated cyclopropanes in good yields. It was found the reaction with alkylmagnesium halide proceeded in the presence of a catalytic amount of manganese(II) chloride.

  用衍生自氯化锰（II）和三当量的格氏试剂或烷基锂的锰酸三烷基酯处理宝石-二溴环丙烷，然后加入亲电试剂以良好的收率提供了二烷基化的环丙烷。发现与烷基卤化镁的反应在催化量的氯化锰（II）的存在下进行。