(R)-(-)-Methyl 3-(p-toluenesulfonate)-2-methylpropionate | 84341-94-6

• 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: (R)-(-)-Methyl 3-(p-toluenesulfonate)-2-methylpropionate
• 英文别名: (R)-methyl 2-methyl-3-[(p-tolylsulfonyl)oxy]propionate；methyl (R)-2-methyl-3-(tosyloxy)propanoate；methyl (R)-2-methyl-3-[(4'-toluenesulfonyl)oxy]propionate；methyl (2R)-2-methyl-3-(4-methylphenyl)sulfonyloxypropanoate
• CAS: 84341-94-6
• 化学式: C₁₂H₁₆O₅S
• 分子量: 272.322
• InChiKey: VPFSEYPRDWJMEF-SNVBAGLBSA-N

物化性质

• 沸点：
  395.2±25.0 °C(Predicted)
• 密度：
  1.217±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  78
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (R)-(-)-Methyl 3-(p-toluenesulfonate)-2-methylpropionate 在 氢氧化钾 、 苄基三乙基氯化铵 、 sodium methylate 、 caesium carbonate 作用下， 以 甲醇 为溶剂， 反应 0.75h， 生成 (S)-methyl 3-(chloromethylthio)-2-methylpropanoate
  参考文献：
  名称：

  Antiviral and antitumor structure-activity relationship studies on tetracyclic eudistomines

  摘要：

  The in vitro antiviral and antitumor activities of (-)-debromoeudistomin K (1a) and 10 structural analogues (1b-1j and 11) were evaluated. The synthesis was accomplished with an intramolecular Pictet-Spengler condensation reaction as the key step. This examination revealed some structural and stereochemical features that are important for both the antiviral and antitumor activities. The most striking points for activity are the necessity to have the correct natural stereochemistry at both C(1) and C(13b) and the presence of the C(1)-NH2 substituent. As was revealed before with naturally isolated eudistomins a substituent in the indole ring greatly influences the biological activity. The 5-OMe derivative Ih shows high potency in both antiviral and antitumor models.

  DOI：

  10.1021/jm00095a019
• 作为产物：
  描述：

  (-)-甲基-D-BATA-羟基异丁酸酯 、 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， 反应 12.0h， 以98%的产率得到(R)-(-)-Methyl 3-(p-toluenesulfonate)-2-methylpropionate
  参考文献：
  名称：

  简易的全合成安非他命T2

  摘要：

  RCM + AD = T2：在存在C16-亚甲基的情况下，区域选择性闭环复分解（RCM）形成了（12 E）-环内双键，该双键经过Os催化的不对称二羟基化（AD）得到所需的12以16个线性步骤全合成Amphidinolide T2所需的，13-二醇中间体，总收率为8.0％。

  DOI：

  10.1002/chem.201001794

文献信息

• Visible light-driven Giese reaction with alkyl tosylates catalysed by nucleophilic cobalt
  作者：Kimihiro Komeyama、Takuya Michiyuki、Yoshikazu Teshima、Itaru Osaka

  DOI：10.1039/d0ra10739e

  日期：——

  The scope of the Giese reaction is expanded using readily available alkyl tosylates as substrates and nucleophilic cobalt(I) catalysts under visible-light irradiation. The reaction proceeds preferentially with less bulky primary alkyl tosylates. This unique reactivity enables the regio-selective Giese reaction of polyol derivatives.

  在可见光照射下，使用容易获得的甲苯磺酸烷基酯作为底物和亲核钴 ( I ) 催化剂，扩大了 Giese 反应的范围。该反应优先使用体积较小的伯烷基甲苯磺酸酯进行。这种独特的反应性使多元醇衍生物的区域选择性吉斯反应成为可能。
• Total Synthesis of Cryptophycin 3
  作者：Paulami Danner、Matthias Bauer、Prodeep Phukan、Martin�E. Maier

  DOI：10.1002/ejoc.200400558

  日期：2005.1

  which contains fragments D and C. After extension at the carboxyl function by esterification with the hydroxy ester 10, the seco compounds 37 and 42 were obtained. Ring closure was achieved by macrolactamization in the presence of TBTU as condensing agent. This work features a streamlined synthesis of the hydroxy ester 10, a short synthesis of the amino acid 14 by enantioselective alkylation of the

  缩肽隐藻素 3 (5) 和隐藻素类似物 43 由相应的四个亚基制备。三肽类似物34从起始氨基酯33获得，其包含片段D和C。通过与羟基酯10酯化在羧基官能团处延伸后，获得seco化合物37和42。在作为缩合剂的 TBTU 存在下，通过大环内酰胺化实现闭环。这项工作的特点是简化了羟基酯 10 的合成，通过甘氨酸亚胺 21 的对映选择性烷基化快速合成了氨基酸 14，以及使用 Fmoc 保护基团保护氨基功能。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
• Asymmetric Syntheses of Potent Antitumor Macrolides Cryptophycin B and Arenastatin A
  作者：Arun K. Ghosh、Alexander Bischoff

  DOI：10.1002/ejoc.200300814

  日期：2004.5

  Efficient and highly stereoselective syntheses of cryptophycin B and arenastatin A, potent cytotoxic agents, are described. An ester-derived titanium enolate mediated syn-aldol reaction was employed to generate the stereocenters C-5 and C-6. The route is convergent and provides a convenient access to the synthesis of structural variants of cryptophycins as well as members of its family.

  描述了有效的细胞毒剂隐藻素 B 和阿那他丁 A 的高效且高度立体选择性的合成。采用酯衍生的钛烯醇化物介导的顺醛醇反应来生成立体中心C-5和C-6。该路线是收敛的，为合成隐藻素及其家族成员的结构变体提供了方便的途径。
• A Convergent Synthesis of (+)-Cryptophycin B, a Potent Antitumor Macrolide from <i>Nostoc</i> sp. Cyanobacteria
  作者：Arun K. Ghosh、Alexander Bischoff

  DOI：10.1021/ol000058i

  日期：2000.6.1

  text] An efficient and highly stereoselective synthesis of cryptophycin B (2), a potent cytotoxic agent, is described. The ester-derived titanium-enolate-mediated syn-aldol reaction was employed to generate the stereocenters C(5) and C(6). The route is convergent and provides a convenient access to the synthesis of structural variants of cryptophycin B as well as members of its family.

  [结构-见正文]描述了一种有效的高度立体选择性的隐藻霉素B（2）（一种有效的细胞毒剂）合成方法。酯衍生的钛烯醇盐介导的顺式羟醛反应被用于生成立体中心C（5）和C（6）。该途径是会聚的，为合成隐藻霉素B及其家族成员的结构变体提供了便利。
• Intramolecular Pictet-Spengler reaction of Nb-Alkoxytryptamines. 4. A study towards diastereocontrol in the synthesis of tetracyclic eudistomins
  作者：Jan H. van Maarseveen、Hans W. Scheeren、Chris G. Kruse

  DOI：10.1016/s0040-4020(01)80376-8

  日期：1993.3

  methylated derivative was also synthesized giving the interesting cis/trans pentacyclic spiro compounds 19 and 20. These results are interpreted in terms of a kinetically favoured electrophilic attack at the indole-3 position, whereas β-carboline formation is the result of a slower route via electrophilic attack at the indole-2 position.

  描述了在合成四环大黄连素中分子内Pictet-Spengler缩合的非对映选择性。N b-烷氧基色胺15a–m与不同大小的基团R 2合成。7成员草硫氮杂ze环的闭合以66–98％的产率完成。使用分子内方法，可以实现非天然反式异构体的非对映选择性。还合成了吲哚甲基化衍生物，得到了有趣的顺式/反式五环螺化合物19和20。这些结果被解释为在吲哚3位置的动力学上有利于亲电子的攻击，而β-咔啉的形成是在吲哚2位置上通过亲电子攻击的较慢途径的结果。