4-(三氟甲氧基)苯基锂 | 334778-36-8

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 卤代烷
• 中文名称: 4-(三氟甲氧基)苯基锂
• 英文名称: 4-(trifluoromethoxy)phenyllithium
• 英文别名: 1-Lithio-4-(trifluoromethoxy)benzene
• CAS: 334778-36-8
• 化学式: C₇H₄F₃LiO
• 分子量: 168.044
• InChiKey: FMYKFTCTERYOJE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.96
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-(三氟甲氧基)苯基锂 在 C₃₃H₃₁O₂Rh 、 双三氟甲烷磺酰亚胺银盐 、 (S)-2-(1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)-3-phenylpropanoic acid 作用下， 以 四氢呋喃 为溶剂， 反应 18.0h， 生成 (R)-2',3'-diphenyl-5'-(trifluoromethoxy)-2H-spiro[benzo[d]isothiazole-3,1'-indene] 1,1-dioxide
  参考文献：
  名称：

  手性Cpx-铑（III）催化的环空对映体对螺环合硫的选择

  摘要：

  手性螺环合剂是有机和药物化学中有价值的化合物类别。快速进入该结构基序需要N-磺酰基酮亚胺和炔烃的[3 + 2]环化。尽管已利用亚氨基基团的CH-H活化的指导基团性质，但相关的不对称变异的发展仍然非常具有挑战性。配备有合适的鸟嘌呤环戊二烯基配体的铑（III）配合物与羧酸添加剂的结合使用，可以使对映体和高收率地获得这类螺环合的阿马替丁。

  DOI：

  10.1002/chem.201504998
• 作为产物：
  描述：

  苯基锂 、 alkaline earth salt of/the/ methylsulfuric acid 以 四氢呋喃 、 联苯 、 正戊烷 为溶剂， 生成 4-(三氟甲氧基)苯基锂
  参考文献：
  名称：

  Relative Basicities of ortho-, meta-, and para-Substituted Aryllithiums

  摘要：

  The relative basicities of aryllithiums bearing methoxy, chlorine, fluorine, trifluoromethyl and trifluoromethoxy substituents at the ortho, meta, and para positions have been assessed. To this end, two aryllithiums of comparable basicity were equilibrated together with the corresponding bromo- or iodoarenes in a 1: 2 mixture of pentanes with tetrahydrofuran at -50, -75, or -100 degrees C. The "basicity" (protodelithiation) increments Delta Delta G derived from the equilibrium constants are linearly correlated with the relative protonation enthalpies of the corresponding aryl anions in the gas phase. However, the correlation factor proves to be position-dependent. Compared with "naked" aryl anions, the basicity of aryllithiums mirrors the effects of ortho, meta, and para substituents to the extent of 36%, 30%, and 25%, respectively.

  DOI：

  10.1021/jo8020083

文献信息

• Process for preparing sil acyclohexane-based liquid crystal compounds from silacyclohexanone compounds
  申请人：SHIN-ETSU CHEMICAL CO., LTD.

  公开号：EP0765880A1

  公开（公告）日：1997-04-02

  Silacyclohexane-based liquid crystal compounds are prepared from a cyclohexanone compound of the following general formula (I) wherein Ar represents a phenyl group or a tolyl group, and R represents a phenyl group, a tolyl group, a linear alkyl group having from 1 to 10 carbon atoms, a mono or difluoroalkyl group having from 1 to 10 carbon atoms, a branched alkyl group having from 3 to 8 carbon atoms or an alkoxyalkyl group having from 2 to 7 carbon atoms, and also from organolithium reagents, followed by hydrogenolysis or hydrogenation after dehydration, with or without further reaction with organometal reagents, and then to de-silylation and reduction.

  基于硅环己烷的液晶化合物是从以下通用式(I)的环己酮化合物制备而成，其中Ar代表苯基或甲苯基，R代表苯基、甲苯基、具有1至10个碳原子的直链烷基、具有1至10个碳原子的单氟或二氟烷基、具有3至8个碳原子的支链烷基或具有2至7个碳原子的烷氧基烷基，然后从有机锂试剂制备，随后脱水后进行氢解或氢化，可以选择进一步与有机金属试剂反应，然后进行脱硅和还原。
• PC-Phos Enabled Catalytic Palladium-heteroallyl Asymmetric Cycloaddition
  作者：Wenge Zhang、Pei-Chao Zhang、Yin-Lin Li、Hai-Hong Wu、Junliang Zhang

  DOI：10.1021/jacs.2c09799

  日期：2022.10.26

  (Pd-OTMM or Pd-NTMM) with cyclic or acyclic 1,3-dienes via a pathway terminated with C–N or C–O bond formation, delivering the highly substituted or fused pyrrolidine and tetrahydrofuran rings in high yields with excellent regio-, diastereo-, and enantioselectivity. Engineering the PC-Phos, one of the chiral sulfinamide phosphine (Sadphos) type ligands, by introducing the di-tert-butyl or/and 3,5-difluorophenyl

  不对称环加成反应是有机化学中快速构建对映体富集环状基序的最有力工具。与通过钯-三亚甲基甲烷 (Pd-TMM) 中间体进行的成熟环加成反应形成鲜明对比的是，杂烯丙基阳离子的杂 (3 + 2) 环加成仍然很少见，这主要是由于它们的热禁性质。据我们所知，目前还没有报道过导致对映体富集的杂环的不对称版本的例子。在这里，我们启用了第一个催化不对称 (3 + 2) 环加成的例子，即通过以 C-N 或 C –O键形成，以高产率提供高度取代或稠合的吡咯烷和四氢呋喃环，具有出色的区域选择性、非对映选择性和对映选择性。通过引入二叔丁基或/和 3,5-二氟苯基是实现优异催化反应性和对映选择性的重要组成部分。
• Keenan, Richard M.; Kruse, Lawrence I., Synthetic Communications, 1989, vol. 19, # 5and6, p. 793 - 798
  作者：Keenan, Richard M.、Kruse, Lawrence I.

  DOI：——

  日期：——
• Cyclohexanone compounds, a process for preparing the cyclohexanone compounds, and a process for preparing silacyclohexane-based compounds from the cyclohexanone compounds
  申请人：Shin-Etsu Chemical Co., Ltd.

  公开号：EP0711777B1

  公开（公告）日：2001-04-04
• Relative Basicities of <i>ortho</i>-, <i>meta</i>-, and <i>para</i>-Substituted Aryllithiums
  作者：Joanna Gorecka-Kobylinska、Manfred Schlosser

  DOI：10.1021/jo8020083

  日期：2009.1.2

  The relative basicities of aryllithiums bearing methoxy, chlorine, fluorine, trifluoromethyl and trifluoromethoxy substituents at the ortho, meta, and para positions have been assessed. To this end, two aryllithiums of comparable basicity were equilibrated together with the corresponding bromo- or iodoarenes in a 1: 2 mixture of pentanes with tetrahydrofuran at -50, -75, or -100 degrees C. The "basicity" (protodelithiation) increments Delta Delta G derived from the equilibrium constants are linearly correlated with the relative protonation enthalpies of the corresponding aryl anions in the gas phase. However, the correlation factor proves to be position-dependent. Compared with "naked" aryl anions, the basicity of aryllithiums mirrors the effects of ortho, meta, and para substituents to the extent of 36%, 30%, and 25%, respectively.