顺式-1-丁基-2-苯基环丙烷 | 64286-53-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 顺式-1-丁基-2-苯基环丙烷
• 英文名称: (2-butylcyclopropyl)benzene
• 英文别名: cis-1-butyl-2-phenylcyclopropane；[(1S,2R)-2-butylcyclopropyl]benzene
• CAS: 64286-53-9
• 化学式: C₁₃H₁₈
• 分子量: 174.286
• InChiKey: HJHWOPNCJJJNDB-CHWSQXEVSA-N

物化性质

• 沸点：
  70 °C(Press: 5 Torr)
• 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 顺式-1-丁基-2-苯基环丙烷
  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)。
• Gold Sulfonium Benzylide Complexes Undergo Efficient Benzylidene Transfer to Alkenes
  作者：Robert G. Carden、Ross A. Widenhoefer

  DOI：10.1002/chem.201902845

  日期：2019.8.22

  gold sulfonium benzylide complexes [(P1)AuCHPh(SR1 R2 )]+  B[3,5-CF3 C6 H3 ]4 }- [P1=P(tBu)2 o-biphenyl; R1 , R2 =-(CH2 )4 - (1 a); R1 =Et, R2 =Ph (1 b); R1 =R2 =Ph (1 c)] were synthesized by reaction of the gold α-chloro benzyl complex (P1)AuCHClPh with sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate and excess sulfide. Complexes 1 undergo efficient benzylidene transfer to alkenes and DMSO under

  sulf金亚苄基络合物[（P1）AuCHPh（SR1 R2）] + B [3,5-CF3 C6 H3] 4}-[P1 = P（tBu）2邻联苯; R1，R2 ＝-（CH2）4-（1a）；R1 = Et，R2 = Ph（1b）；通过金α-氯苄基络合物（P1）AuCHClPh与四[3,5-双（三氟甲基）苯基]硼酸钠和过量的硫化物反应合成R1 = R2 = Ph（1 c）]。配合物1在温和的条件下无需外部活化即可有效地将亚苄基转移至烯烃和DMSO。1 c与苯乙烯反应的动力学分析与阳离子金亚苄基络合物[（P1）AuCHPh] +（I）的中间体一致。
• 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。
• 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。
• Substituent Effects and the Mechanism of Gold to Alkene Benzylidene Transfer Employing a Gold Sulfonium Benzylide Complex
  作者：Mitch Rivers、Robert G. Carden、Ross A. Widenhoefer

  DOI：10.1021/acs.organomet.2c00097

  日期：2022.5.9

  sulfonium benzylide complex [(P)AuCHPh(SPh2)]+ B [3,5-CF3C6H3]4}− [P = P (t-Bu)2o-biphenyl; 1] at room temperature via the cationic two-coordinate gold benzylidene complex [(P)AuCHPh]+ (I) to form phenyclyclopropanes. The reactivity of p-substituted vinyl arenes toward I decreased with the decreasing electron donor ability of the vinyl arene (ρ = −1.49 ± 0.15), and the reactivity of aliphatic alkenes

  脂肪族和芳香族烯烃与金锍苄基络合物 [( P )AuCHPh(SPh 2 )] + B [3,5-CF 3 C 6 H 3 ] 4 } - [ P = P ( t -Bu ) 2邻联苯；1 ] 在室温下通过阳离子双配位金亚苄基配合物[( P )AuCHPh] + ( I ) 生成苯环丙烷。对位取代乙烯基芳烃对I的反应性随着乙烯基芳烃的电子供体能力降低（ρ = -1.49 ± 0.15），脂肪族烯烃对I的反应性在很大程度上取决于连接到更多取代烯烃末端的烷基数量。亚苄基向顺式和反式-β-甲基苯乙烯的转移发生，烯烃构型完全保留。亚苄基转移到乙烯基芳烃导致顺式的主要形成-环丙烷（dr = 4.1:1 至 13.9:1），而亚苄基转移至脂肪族烯烃的选择性通常较低（dr = 1.3:1 至 5.1:1）。我们所有的实验观察结果都与协调的、异步的、亲电的亚苄基转移机制一致。亚苄基转移的非对映选择性是在