tert-butyl 2-methyl-2-phenylcyclopropane-1-carboxylate

• 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: tert-butyl 2-methyl-2-phenylcyclopropane-1-carboxylate
• 英文别名: t-butyl cis-2-methyl-2-phenylcyclopropane-1-carboxylate；tert-butyl (1S,2R)-2-methyl-2-phenylcyclopropane-1-carboxylate
• 化学式: C₁₅H₂₀O₂
• 分子量: 232.323
• InChiKey: FJLRCMXDXGEMIW-DOMZBBRYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  重氮基乙酸叔丁酯 、 2-苯基-1-丙烯 在 C₆₇H₅₁IrN₂O₂ 作用下， 以 四氢呋喃 为溶剂， 反应 24.17h， 生成 tert-butyl trans-2-methyl-2-phenylcyclopropane-1-carboxylate 、 tert-butyl 2-methyl-2-phenylcyclopropane-1-carboxylate
  参考文献：
  名称：

  芳基铱-Salen配合物的构建：共轭和非共轭烯烃的对映和顺式选择性环丙烷化

  摘要：

  通过 S(E)Ar 机制分别在顶端引入甲苯基或苯基配体，合成了两种稳定且具有旋光活性的铱-salen 配合物，发现它们是顺式选择性不对称环丙烷化的有效催化剂。环丙烷化的范围很广，不仅共轭单、二、三取代烯烃的反应，而且非共轭末端烯烃的反应都具有很高的对映选择性和顺式选择性，即使在存在官能团如醚或酯。8-[(1R,2S)-2-己基环丙基]辛酸酯的短步合成证明了该环丙烷化的效用，该合成从大肠杆菌B-ATCC 11303中分离，使用该反应作为关键步骤。

  DOI：

  10.1021/ja802561t

文献信息

• Highly Enantioselective Cyclopropanation with Co(II)-Salen Complexes: Control ofcis- andtrans-Selectivity by Rational Ligand-Design
  作者：Tatsuo Niimi、Tatsuya Uchida、Ryo Irie、Tsutomu Katsuki

  DOI：10.1002/1615-4169(20010129)343:1<79::aid-adsc79>3.0.co;2-8

  日期：2001.1.29

  Cyclopropanation of styrene derivatives with alkyl α-diazoacetate in the presence of the second-generation (salen)cobalt(II) complex 6 proceeded with excellent cis- and enantioselectivity. On the other hand, the cyclopropanation in the presence of complex 14 which was designed on the basis of the mechanism of asymmetric induction by complex 6 showed good trans- and excellent enantioselectivity.

  在第二代（salen）钴（II）配合物6的存在下，用α-重氮乙酸烷基酯对苯乙烯衍生物的环丙烷化反应具有优异的顺式和对映选择性。另一方面，根据配合物6的不对称诱导机理设计的在配合物14存在下的环丙烷化显示出良好的反式和优异的对映选择性。
• Highly Enantioselective Cyclopropanation of Styrenes and Diazoacetates Catalyzed by 3-Oxobutylideneaminatocobalt(II) Complexes, Part 1. Designs of Cobalt Complex Catalysts and the Effects of Donating Ligands
  作者：Taketo Ikeno、Mitsuo Sato、Hiroyuki Sekino、Asae Nishizuka、Tohru Yamada

  DOI：10.1246/bcsj.74.2139

  日期：2001.11

  Highly enantioselective cyclopropanation of styrene derivatives and diazoacetates was effectively catalyzed by reasonably designed 3-oxobutylideneaminatocobalt(II) complexes, whose ligands were prepared from 1,2-dimesitylethylenediamine and alkyl 3-oxobutanoates. The steric demand of the diamine unit of the complexes seriously influenced the enantioselectivity, and the ester groups on their side chains

  合理设计的 3-氧代亚丁基氨基钴 (II) 配合物可有效催化苯乙烯衍生物和重氮乙酸酯的高对映选择性环丙烷化，其配体由 1,2-二甲基亚乙基二胺和 3-氧代丁酸烷基酯制备。配合物二胺单元的空间需求严重影响了对映选择性，其侧链上的酯基在一定程度上提高了反式选择性。添加催化量的 N-甲基咪唑显着加速了反应并提高了对映选择性，因为它作为轴向配体与配合物的中心钴原子配位。醇或含水醇溶剂对于 1-取代的 1-苯基乙烯的环丙烷化也特别有效，以在含水甲醇中实现高对映选择性。
• Concave Reagents 32: <i>syn</i>- and <i>anti</i>-Selective Cyclopropanation of Alkenes with Diazoacetates Catalyzed by Copper (i) Complexes of Concave 1,10-Phenanthrolines
  作者：Frank Löffler、Martin Hagen、Ulrich Lüning

  DOI：10.1055/s-1999-3171

  日期：1999.11

  Two classes of concave 1,10-phenanthroline ligands 1 and 2 have been used in the copper(i) catalyzed cyclopropanation of several acyclic and cyclic alkenes 3 with three diazoacetates 4-6. The bimacrocyclic 2,9-diaryl-1,10-phenanthrolines 1 favor the anti-(trans- or exo-) cyclopropanation with anti/syn-selectivities of up to >99 : 1 (8g). In contrast, with the 1,10-phenanthroline bridged calix[6]arenes 2 as ligands a rarely observed syn-selective cyclopropanation was achieved. Methyl diazoacetate (6) showed the best syn-selectivities with anti/syn-ratios of up to 14 : 86 (9g).

  两类凹面1,10-菲咯啉配体1和2被用于铜(I)催化的数种非环和环烯烃3与三种二氮乙酸酯4-6的环丙烯化反应。双大环2,9-二芳基-1,10-菲咯啉1倾向于反（顺式或外源性）环丙烯化，具有高达>99 : 1的反/顺选择性（8g）。相比之下，使用1,10-菲咯啉桥接的贵族[6]芳烃配体2时，获得了罕见的顺选择性环丙烯化。甲基二氮乙酸酯（6）显示出最佳的顺选择性，反/顺比高达14 : 86（9g）。
• From homogeneously to heterogeneously catalyzed cyclopropanation reactions: New polymeric membranes embedding cobalt chiral schiff base complexes
  作者：Alessandro Caselli、Maria Giovanna Buonomenna、Federico de Baldironi、Luca Laera、Simone Fantauzzi、Fabio Ragaini、Emma Gallo、Giovanni Golemme、Sergio Cenini、Enrico Drioli

  DOI：10.1016/j.molcata.2009.10.024

  日期：2010.2

  In this paper we report the preparation of catalytic polymeric membranes having the complex [(N,N'-bis(3-tert-butyl-5-(heptadecafluorooctyl)salicylidene)-trans-1,2-cyclohexanediamine )Co] embedded into Hyflon AD60X, PES and PSf and their use in the cyclopropanation reaction of olefins with ethyl diazoacetate (EDA). A study of the reaction in the homogeneous phase was also performed. The kinetics of the cyclopropanation reaction is first-order in the diazoacetate and the catalyst and zero order in the olefin, but we observed a more complex dependence on the additive, NMI (N-methylimidazole). The positive effect of the additive is completely reversed at NMI concentration higher than 6.10(-2) M. (C) 2009 Elsevier B.V. All rights reserved.
• Catalyst structure and the enantioselective cyclopropanation of alkenes by copper complexes of biaryldiimines: the importance of ligand acceleration
  作者：Christopher J Sanders、Kevin M Gillespie、Peter Scott

  DOI：10.1016/s0957-4166(01)00157-4

  日期：2001.5

  The use of chiral non-racemic biaryl copper(I) complexes in the enantioselective cyclopropanation of a number of olefins with either ethyl or tert-butyl diazoacetate: is described. Lack of ligand acceleration and the presence of equilibrium amounts of catalytically active uncomplexed Cu(I) ions account for lowered enantioselectivity when using certain ligands. (C) 2001 Elsevier Science Ltd. All rights reserved.