methyl (E)-2-methyl-5-phenyl-2-(p-toluenesulfonylamino)pent-4-enoate | 503838-97-9

• 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: methyl (E)-2-methyl-5-phenyl-2-(p-toluenesulfonylamino)pent-4-enoate
• 英文别名: methyl (E)-2-methyl-2-[(4-methylphenyl)sulfonylamino]-5-phenylpent-4-enoate
• CAS: 503838-97-9
• 化学式: C₂₀H₂₃NO₄S
• 分子量: 373.473
• InChiKey: SINLCYXPDSXLEV-JXMROGBWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  26
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  80.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl (E)-2-methyl-5-phenyl-2-(p-toluenesulfonylamino)pent-4-enoate 在 碘 作用下， 以 乙腈 为溶剂， 反应 16.0h， 以80%的产率得到4-Iodo-2-methyl-5-phenyl-1-(toluene-4-sulfonyl)-pyrrolidine-2-carboxylic acid methyl ester
  参考文献：
  名称：

  通过5-内-trig碘环化快速合成高度取代的脯氨酸类似物

  摘要：

  在碱存在或不存在的情况下，高度取代的α-烯基-α-氨基酯均会经历平滑的5-内-碘环化反应，从而使取代的脯氨酸衍生物的产率高至优异。立体选择性通常仅适中，​​除非氨基酯残基带有在其α位分支的取代基。

  DOI：

  10.1016/j.tetlet.2006.02.017
• 作为产物：
  描述：

  ethyl 2-amino-2-methyl-5-phenyl-4-pentenoate 、 对甲苯磺酰氯 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以1.3 g的产率得到methyl (E)-2-methyl-5-phenyl-2-(p-toluenesulfonylamino)pent-4-enoate
  参考文献：
  名称：

  Carbenium ion trapping using sulfonamides: an acid-catalysed synthesis of pyrrolidines by intramolecular hydroamination

  摘要：

  Cyclisations of homoallylic sulfonamides proceed smoothly via carbenium ion generation using trifluoromethanesulfonic (triflic) acid, the ease of cyclisation being directly related to the ion stability to give good to excellent yields of the corresponding pyrrolidines. Both toluene- and nitrophenyl-sulfonyl groups are suitable for all substrates tested whereas the corresponding carbamates are only useful in cases of tertiary and highly stabilised carbenium ions. Polyene-derived sulfonamides can also be cyclised to the corresponding polycyclic systems in remarkably high yields, in reactions reminiscent of related cascades encountered in terpene biosynthesis. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.03.107

文献信息

• A Cross-Metathesis Route to Functionalized α-Methyl α-Substituted Amino Acids
  作者：Roy P. M. Storcken、Lavinia Panella、Floris L. van Delft、Bernard Kaptein、Quirinus B. Broxterman、Hans E. Schoemaker、Floris P. J. T. Rutjes

  DOI：10.1002/adsc.200600446

  日期：2007.1.8

  A chemoenzymatic approach to the synthesis of functionalized α-methyl α-substituted amino acids is detailed. This involves amidase-mediated enzymatic resolution of α-methyl α-substituted side-chain ω-unsaturated amino acids followed by functionalization via cross-metathesis.

  用化学酶方法合成功能化的α-甲基α-取代的氨基酸。这涉及酰胺酶介导的α-甲基α-取代的侧链ω-不饱和氨基酸的酶促拆分，然后通过交叉复分解进行功能化。
• Sulfonamides as novel terminators of cationic cyclisations
  作者：Charlotte M. Haskins、David W. Knight

  DOI：10.1039/b207755h

  日期：2002.11.4

  Trifluoromethanesulfonic (triflic) acid is an excellent catalyst for inducing overall 5-endo cyclisation of homoallylic sulfonamides [e.g.4] to give pyrrolidines [e.g.5]. In competitive experiments, pyrrolidines or homopiperidines are formed in preference to piperidines, even when the latter would be obtained by trapping a tertiary carbocation. Cationic cascades terminated by a sulfonamide group are viable for the efficient formation of polycyclic systems.

  三氟甲磺酸（三氟甲基磺酸）是一种极好的催化剂，可诱导均烯丙基磺酰胺（如 4）发生整体 5-endo 环化反应，生成吡咯烷类化合物（如 5）。在竞争性实验中，吡咯烷或同哌啶类化合物比哌啶类化合物更容易形成，即使后者是通过捕获一个叔碳位而得到的。以磺酰胺基团终止的阳离子级联可以有效地形成多环体系。
• On the rapid synthesis of highly substituted proline analogues by 5-endo-trig iodocyclisation
  作者：Muhammad Amjad、David W. Knight

  DOI：10.1016/j.tetlet.2006.02.017

  日期：2006.4

  Highly substituted α-alkenyl-α-amino esters undergo smooth if rather slow 5-endo-iodocyclisations both in the presence or absence of base to give good to excellent yields of substituted proline derivatives. The stereoselectivities are often only moderate, except when the amino ester residue carries a substituent, which is branched at its α-position.

  在碱存在或不存在的情况下，高度取代的α-烯基-α-氨基酯均会经历平滑的5-内-碘环化反应，从而使取代的脯氨酸衍生物的产率高至优异。立体选择性通常仅适中，​​除非氨基酯残基带有在其α位分支的取代基。
• Carbenium ion trapping using sulfonamides: an acid-catalysed synthesis of pyrrolidines by intramolecular hydroamination
  作者：Charlotte M. Griffiths-Jones (née Haskins)、David W. Knight

  DOI：10.1016/j.tet.2010.03.107

  日期：2010.6

  Cyclisations of homoallylic sulfonamides proceed smoothly via carbenium ion generation using trifluoromethanesulfonic (triflic) acid, the ease of cyclisation being directly related to the ion stability to give good to excellent yields of the corresponding pyrrolidines. Both toluene- and nitrophenyl-sulfonyl groups are suitable for all substrates tested whereas the corresponding carbamates are only useful in cases of tertiary and highly stabilised carbenium ions. Polyene-derived sulfonamides can also be cyclised to the corresponding polycyclic systems in remarkably high yields, in reactions reminiscent of related cascades encountered in terpene biosynthesis. (C) 2010 Elsevier Ltd. All rights reserved.