1-(p-toluenesulphonyl)-3-methylimidazolium triflate

• 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: 1-(p-toluenesulphonyl)-3-methylimidazolium triflate
• 英文别名: 1-(toluenesulfonyl)-3-methylimidazolium triflate；1-(toluenesulphonyl)-3-methylimidazolium triflate；1-methyl-3-[(4-methylbenzene)sulfonyl]imidazol-1-ium triflate；1-(p-toluenesulfonyl)-3-methylimidazolium triflate；1-p-Toluenesulfonyl-3-methylimidazolium triflate；1-methyl-3-(4-methylphenyl)sulfonylimidazol-1-ium;trifluoromethanesulfonate
• 化学式: CF₃O₃S*C₁₁H₁₃N₂O₂S
• 分子量: 386.373
• InChiKey: FTJAOAGVFFMGDE-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  0.91
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  117
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  1-(p-toluenesulphonyl)-3-methylimidazolium triflate 在 N-甲基咪唑 、 sodium hydroxide 、 三氟乙酸 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 18.83h， 生成 (2SR,3RS,4RS)-3-(2-hydroxyethyl)-4-(toluene-4-sulfonyloxy)pyrrolidine-1,2-dicarboxylic acid 1-benzyl ester
  参考文献：
  名称：

  以aza- [2,3] -Wittigσ重排为关键立体化学确定步骤的（+/-）-海藻酸的全合成。

  摘要：

  由3-丁炔-1-醇合成（+/-）-海藻酸举例说明了通往类胡萝卜素骨架的灵活途径。该路线依赖于aza- [2,3] -Wittigσ重排，以有效地在C2-C3之间安装相对立体化学。C4立体中心源自非对映控制的碘内酯化。氮杂-[2，3]-维蒂希重排潜在地允许C3处的结构多样性，并且保持立体化学的甲苯磺酰基基团的置换允许C4处的结构多样性。发现在用高阶氰基铜酸盐试剂处理后，反式-C2羧酸官能团对于保持立体化学在C4上是最重要的。

  DOI：

  10.1021/jo030101q
• 作为产物：
  描述：

  对甲苯磺酰氯 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 1-(p-toluenesulphonyl)-3-methylimidazolium triflate
  参考文献：
  名称：

  In search of diamine analogs of the α,α-diphenyl prolinol privileged chiral organocatalyst. Synthesis of diamine derivatives of α,α-diphenyl-(S)-prolinol and their application as organocatalysts in the asymmetric Michael and Mannich reactions

  摘要：

  This paper describes improved reaction conditions for the substitution of the hydroxyl group in (S)-diphenyl(pyrrolidin-2-yl)methanol by the azide group, which was then reduced to the diamine derivative. We examined two protecting groups (N-Bn and N-Boc) on the pyrrolidine nitrogen in order to functionalize the primary amino group into various amide, alkylated amine, sulfonamide, thiourea and triazole derivatives. Notably, carefully controlled conditions were required to generate the desired derivatives from the sterically hindered benzhydrylamine moiety. Unexpectedly, upon removal of the N-protecting group in derivatives containing electrophilic polar double bonds (C=S, C=O) cyclization took place, affording products such as amidines. The target compounds were evaluated as bifunctional organocatalysts in the asymmetric Michael and Mannich addition reactions. (S)-2-(Azidodiphenylmethyl) pyrrolidine (S)-7 was identified as the most efficient organocatalyst among the various diamine derivatives of alpha,alpha-diphenyl-(S)-prolinol prepared in this work. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.11.032

文献信息

• Synthesis of Rh(I) Complexes Bearing<i>N</i>-<i>p</i>-Toluenesulfonyl-substituted<i>N</i>-Heterocyclic Carbenes
  作者：Tetsuo Sato、Daisuke Yoshioka、Yoichi Hirose、Shuichi Oi

  DOI：10.1246/cl.130979

  日期：2014.3.5

  We have synthesized Rh(I) complexes bearing a 1,2,4-triazol-3-ylidene or imidazol-2-ylidene substituted N-p-toluenesulfonyl (N-Ts) group. Structural characterizations of the Rh(I) complexes revealed that, because of its mesomeric and inductive electron-withdrawing effects, the N-Ts substituent increased π-accepting ability and decreased σ-donating ability of carbenes compared to N-mesityl substituents.

  我们合成了带有1,2,4-三唑-3-亚基或咪唑-2-亚基取代的对甲苯磺酰胺（N-Ts）基团的铑(I)配合物。对铑(I)配合物的结构表征揭示了由于N-Ts取代基的共轭和诱导吸电子效应，与N-甲基取代基相比，增强了卡宾的π接受能力并降低了σ给予能力。
• Synthesis of (2S, 3R, 4S), (2S, 3S, 4R)-epoxyprolines and aminohydroxyprolines
  作者：J. Kenneth Robinson、Victor Lee、Timothy D.W. Claridge、Jack E. Baldwin、Christopher J. Schofield

  DOI：10.1016/s0040-4020(97)10352-0

  日期：1998.1

  2S, 3R, 4S- and 2S, 3S, 4R-epoxy-L-prolines were synthesised from trans-4-hydroxy-L-proline. Assignment of the stereochemical configurations of the epoxy prolines was achieved by n.O.e. studies and chemical correlation. The synthetic utility of the protected epoxides was investigated briefly by ring opening with NaN3, followed by deprotection to give aminohydroxy prolines.

  2小号，3 - [R，4小号-和2小号，3小号，4 - [R -环氧大号-prolines从合成反式-4-羟基-大号脯氨酸。环氧脯氨酸的立体化学构型的分配是通过nOe研究和化学相关性实现的。通过用NaN 3开环，然后脱保护得到氨基羟脯氨酸，简要地研究了被保护的环氧化物的合成效用。
• Cycloadditions of Nonstabilized 2-Azaallyllithiums with Cycloheptatriene
  作者：William H. Pearson、Douglas M. Mans、Jeff W. Kampf

  DOI：10.1021/ol026423i

  日期：2002.9.1

  [reaction: see text] Transmetalation of tin-bearing cyclic imidates gave 2-azaallyllithiums that underwent [pi6s + pi4s] cycloadditions with cycloheptatriene to produce tricyclic adducts, which may be useful as analogs of cocaine. The peri- and stereoselectivity of this process are discussed.

  [反应：见正文]含锡环状酰亚胺的重金属化生成了2-氮杂烯丙基锂，该二氮杂烯丙基锂与环庚三烯进行了[pi6s + pi4s]环加成反应，生成三环加合物，可用作可卡因的类似物。讨论了该过程的周和立体选择性。
• Substrate specificity of proline-4-hydroxylase: Chemical and enzymatic synthesis of 2S,3R,4S-epoxyproline
  作者：Jack E. Baldwin、Robert A. Field、Christopher C. Lawrence、Victor Lee、J.Kenneth Robinson、Christopher J. Schofield

  DOI：10.1016/s0040-4039(00)60753-0

  日期：1994.6

  The substrate specificity of L-proline 4-hydroxylase, a 2-oxoglutarate dependent dioxygenase from Streptomyces griseoviridus P8648, was investigated. Preliminary assays measuring turnover of 2-oxoglutarate indicated 3,4-dehydro-L-proline was an efficient substrate. The identity of the product was shown to be 2S,3R,4S-epoxy-L-proline by comparison with synthetic 2S,3R,4S- and 2S,3S,4R-epoxy-L-prolines.