trans-1-(p-chlorobenzoyl)-2-phenylcyclopropane | 63016-92-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: trans-1-(p-chlorobenzoyl)-2-phenylcyclopropane
• 英文别名: (±)-(E)-(4-chlorophenyl)(2-phenylcyclopropyl)methanone；trans-1-p-Chlorbenzoyl-2-phenylcyclopropan；(4-chlorophenyl)-[(1S,2S)-2-phenylcyclopropyl]methanone
• CAS: 63016-92-2
• 化学式: C₁₆H₁₃ClO
• 分子量: 256.732
• InChiKey: SESAUKNQPZECGG-CABCVRRESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  trans-1-(p-chlorobenzoyl)-2-phenylcyclopropane 在 二-叔-丁基过氧草酸酯 、 1,3-二甲基-2-苯基-2H-苯并咪唑 作用下， 以 乙腈 为溶剂， 反应 23.0h， 以0.28%的产率得到(1SR,2SR)-phenyl(2-phenylcyclopropyl)ketone
  参考文献：
  名称：

  Reversible cyclopropyl ring opening of 1-aroyl-2-phenylcyclopropane radical anions. Determination of the ring opening and closure rates of the intermediate ketyls

  摘要：

  The phenylcyclopropylketyl ring opening has been used as a mechanistic probe for the detection of radical intermediates. The reaction is of limited use since the ring-opening reaction is reversible. 1-Benzoyl-2-phenylcyclopropane (II) was considered to be a better probe since the ring opening of its radical anion was believed to be irreversible. In this study, the ring opening of II.- is also found to be reversible since the radical-initiated reduction of (+)-trans-1-benzoyl-2-phenylcyclopropane ((+)-trans-II) with 1,3-dimethyl-2-phenylbenzimidazoline (DMBI) leads to racemized and isomerized products ((+)-trans-11 and (+/-)-cis-II). The rate constants (k(o)) for the ring opening of both trans- and cis-II ketyls have been estimated from the intramolecular competitive reduction of both trans- and cis-1-(p-chlorobenzoyl)-2-phenylcyclopropane with DMBI (k(o,trans) = (2.8 +/- 0. 1) x 10(5) s-1, k(o, cis) = (1.6 +/- 0.2) x 10(6) s-1, 22-degrees-C). The rate constants for the ring closure (k(c)) of the opened radical to give the trans and cis ketyls were estimated from the DMBI reduction of trans-II using dicyclohexylphosphine as a hydrogen atom donor (k(c,trans) = 4 x 10(2) s-1, k(c,cis) = 23 +/- 9 s-1, 61-degrees-C).

  DOI：

  10.1021/ja00028a045
• 作为产物：
  描述：

  对氯苯乙酮 在 sodium hydride 、 sodium hydroxide 作用下， 以 乙醇 、 水 、 二甲基亚砜 、 mineral oil 为溶剂， 反应 1.0h， 生成 trans-1-(p-chlorobenzoyl)-2-phenylcyclopropane
  参考文献：
  名称：

  对映选择性铜催化乙烯基环丙烷的1,5-氰基三氟甲基化

  摘要：

  乙烯基自由基丙烷的铜催化对映选择性1,5-氰基三氟甲基化反应已采用自由基中继策略开发。这种不对称反应显示出高对映选择性控制，较宽的底物范围和温和的条件。由Togni试剂原位生成的CF 3基团引发，该方法为烯烃的远程对映选择性双官能化提供了新的解决方案，因此为合成手性含CF 3的内部烯基腈提供了直接的方法。

  DOI：

  10.1021/acs.orglett.9b03012

文献信息

• Iron-Catalyzed Hydroboration of Vinylcyclopropanes
  作者：Chenhui Chen、Xuzhong Shen、Jianhui Chen、Xin Hong、Zhan Lu

  DOI：10.1021/acs.orglett.7b02691

  日期：2017.10.6

  An iron-catalyzed hydroboration of vinylcyclopropane with HBpin is first reported for the preparation of valuable homoallylic organoboronic esters. The iron catalysts enable efficient and regioselective C–C cleavage of vinylcyclopropanes, stereoselectively delivering E-alkenes with good stereospecific selectivity at an allylic position. This protocol exhibits mild conditions with good functional group

  首次报道了用HBpin对乙烯基环丙烷进行铁催化的硼氢化反应，以制备有价值的均烯丙基有机硼酸酯。铁催化剂可实现乙烯基环丙烷的高效和区域选择性C–C裂解，在烯丙基位置立体选择性地提供具有良好立体选择性的E-烯烃。该协议显示了温和的条件，具有良好的官能团耐受性。手性均烯丙基有机硼酸酯可以进一步转化为手性多取代的四氢呋喃和四氢吡喃。
• Catalytic Asymmetric Cyclopropanation of Enones with Dimethyloxosulfonium Methylide Promoted by a La−Li₃−(Biphenyldiolate)₃ + NaI Complex
  作者：Hiroyuki Kakei、Toshihiko Sone、Yoshihiro Sohtome、Shigeki Matsunaga、Masakatsu Shibasaki

  DOI：10.1021/ja076797c

  日期：2007.11.1

  Catalytic asymmetric cyclopropanation of enones with dimethyloxosulfonium methylide using a La−Li3−(biphenyldiolate)3 + NaI complex is described. The present method is complementary to the previously reported catalytic enantioselective methods in terms of ylides used, and trans products were exclusively obtained in good yield (96−73%) and high enantioselectivity (99−84% ee). Use of biphenyldiol 1b-H2

  描述了使用 La−Li3−(biphenyldiolate)3 + NaI 复合物对烯酮与二甲基氧锍甲基化物的催化不对称环丙烷化反应。本方法在使用的叶立德方面是对先前报道的催化对映选择性方法的补充，并且反式产物仅以良好的产率 (96-73%) 和高对映选择性 (99-84% ee) 获得。联苯二醇 1b-H2 和 NaI 添加剂的使用对于实现高对映选择性至关重要。
• Mechanochemical Simmons–Smith cyclopropanation<i>via</i>ball-milling-enabled activation of zinc(0)
  作者：Lorenzo Pontini、Jamie A. Leitch、Duncan L. Browne

  DOI：10.1039/d3gc00649b

  日期：——

  The bulk solvent-free synthesis of cyclopropanesviaa ball-milling-enabled Simmons–Smith reaction is herein described.

  本文介绍了通过球磨西蒙斯-史密斯反应无溶剂合成环丙烷的方法。
• Synthesis of acylcyclopropanes and oxiranes from vinylsulfonium salts and lithium enolates
  作者：Ken Takaki、Toshio Agawa

  DOI：10.1021/jo00440a024

  日期：1977.9
• Enantioselective Copper-Catalyzed 1,5-Cyanotrifluoromethylation of Vinylcyclopropanes
  作者：Zi-Qi Zhang、Xiang-Yu Meng、Jie Sheng、Quan Lan、Xi-Sheng Wang

  DOI：10.1021/acs.orglett.9b03012

  日期：2019.10.18

  A copper-catalyzed enantioselective 1,5-cyanotrifluoromethylation of vinylcyclopropanes has been developed using a radical relay strategy. This asymmetric reaction has demonstrated high enantioselective control, broad substrate scope, and mild conditions. Initiated by the in situ generated CF3 radical from Togni’s reagent, this method offers a new solution for remote enantioselective bifunctionalization

  乙烯基自由基丙烷的铜催化对映选择性1,5-氰基三氟甲基化反应已采用自由基中继策略开发。这种不对称反应显示出高对映选择性控制，较宽的底物范围和温和的条件。由Togni试剂原位生成的CF 3基团引发，该方法为烯烃的远程对映选择性双官能化提供了新的解决方案，因此为合成手性含CF 3的内部烯基腈提供了直接的方法。