2-benzyl-2-methylbut-3-enoic acid | 180902-61-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 苯丙酸
• 英文名称: 2-benzyl-2-methylbut-3-enoic acid
• CAS: 180902-61-8
• 化学式: C₁₂H₁₄O₂
• 分子量: 190.242
• InChiKey: CVUXKGMBXIMRJH-UHFFFAOYSA-N

物化性质

• 沸点：
  307.3±11.0 °C(Predicted)
• 密度：
  1.068±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-benzyl-2-methylbut-3-enoic acid 在 ammonium hydroxide 、 lithium aluminium tetrahydride 、 甲酸 、 双氧水 作用下， 反应 44.67h， 生成 N-propyl-2-benzyl-3,4-dihydroxy-2-methylbutanamide
  参考文献：
  名称：

  Gavina, Pablo; Lavernia, Natividad Lopez; Mestres, Ramon, Journal of Chemical Research, Miniprint, 1996, # 6, p. 1533 - 1553

  摘要：

  DOI：
• 作为产物：
  描述：

  2-苄基-2-甲基-3-氧代丁酸甲酯 在 吡啶 、 sodium tetrahydroborate 、 氯化亚砜 作用下， 以 甲醇 、 水 为溶剂， 反应 49.0h， 生成 2-benzyl-2-methylbut-3-enoic acid
  参考文献：
  名称：

  Syntheses and Kinetic Evaluation of Racemic and Optically Active 2-Benzyl-2-methyl-3,4-epoxybutanoic Acids as Irreversible Inactivators for Carboxypeptidase A

  摘要：

  Racemic and optically active 2-benzyl-2-methyl-3,4-epoxybutanoic acids were synthesized and evaluated as inactivators for carboxypeptidase A. a representative zinc-containing proteolytic enzyme. Only the threo-form of the inactivator is effective and its potency in terms of k(inact)/K-I value is lower by 42-fold compared with 2-benzyl-3,4-epoxybutanoic acid, indicating that the alpha-methyl group affects adversely in the inactivation contrary to the expectation that it would enhance the inactivation activity of the inhibitor through additional interactions of the methyl group with a small cavity (alpha-methyl hole) present next to the S-1' hydrophobic pocket. Of the enantiomeric pair, the inactivator having the (2S,3R)-configuration is more potent than its enantiomer by 44-fold. The observed kinetic results may be rationalized on the basis that the methyl group in the inactivator having the (2R,3S)configuration experiences the van der Waals repulsive interactions with the bottom of the active site crevice in binding to CPA, casting a doubt on the presence of the so-called alpha-methyl hole at the active site of carboxypeptidase A. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0968-0896(01)00340-6

文献信息

• Alkylation of lithium dienediolates of butenoic acids. Regioselectivity effects of structure and leaving group of the alkylating agent
  作者：Maria J. Aurell、Salvador Gil、Ramon Mestres、Margarita Parra、Lilian Parra

  DOI：10.1016/s0040-4020(98)00149-5

  日期：1998.4

  Regioselectivity of alkylation of but-2-enoic acids 1 and 2 by alkyl halides strongly depends on the reactivity of the electrophile. High α selectivity results for saturated alkyl halides, whereas poor α-selectivity is obtained for highly reactive allyl and benzyl halides. For reactive alkylating halides selectivity is partly governed by the ion pairing aggregates of the dienediolates. Lithium bromide

  丁-2-烯酸1和2被烷基卤化物烷基化的区域选择性在很大程度上取决于亲电试剂的反应性。饱和烷基卤化物的α选择性高，而高反应性烯丙基卤和苄基卤的α选择性差。对于反应性烷基化卤化物，选择性部分地由二烯二醇的离子对聚集体决定。正在进行的反应中生成的溴化锂和羧酸盐对区域选择性产生相反的影响。
• New conditions for the generation of dianions of carboxylic acids
  作者：Eva M. Brun、Isabel Casades、Salvador Gil、Ramón Mestres、Margarita Parra

  DOI：10.1016/s0040-4039(98)01050-8

  日期：1998.7

  Lithium carboxylic acid enediolates are generated efficiently using lithium amides prepared from thienyllithium or butyllithium and either diethylamine, piperazine, N,N′-dibenzylethylenediamine, N-benzylpiperazine or 1,3,3-trimethyl-6-azabicyclo[3.2.1]octane, even in catalytic amounts.

  使用由噻吩基锂或丁基锂与二乙胺，哌嗪，N，N'-二苄基乙二胺，N-苄基哌嗪或1,3,3-三甲基-6-氮杂双环[3.2.1]辛烷制备的酰胺化锂可有效生成羧酸烯二醇锂即使是催化量。
• Regiocontrol in Alkylation of Lithium Dienediolates of Unsaturated Carboxylic Acids
  作者：Eva M. Brun、Salvador Gil、Margarita Parra

  DOI：10.1055/s-2001-9721

  日期：——

  Alkylation of dienediolates from unsaturated carboxylic acids with benzylic halides often results in mixtures of regioisomers. However it can be controlled by adequate modification of the reaction conditions. Thus, addition of DMI leads mainly to the α-regioisomer, whereas addition of 12-crown-4 allows to obtain the γ-regioisomer as the major product from the same reactants.

  用苄基卤化物对来自不饱和羧酸的二烯二醇盐进行烷基化，通常会导致区域异构体混合物的产生。然而，这可以通过对反应条件的适当改良来控制。因此，加入DMI主要导致α-区域异构体的生成，而加入12-冠-4则允许从相同反应物中获得作为主要产物的γ-区域异构体。
• Modular Synthesis of Benzocyclobutenes via Pd(II)-Catalyzed Oxidative [2+2] Annulation of Arylboronic Acids with Alkenes
  作者：Takuji Fujii、Simone Gallarati、Clémence Corminboeuf、Qian Wang、Jieping Zhu

  DOI：10.1021/jacs.2c03565

  日期：2022.5.25

  We report herein an efficient synthesis of diversely functionalized BCBs by a Pd(II)-catalyzed formal [2+2] annulation between arylboronic acids and alkenes in the presence of N-fluorobenzenesulfonimide (NFSI). An intermolecular carbopalladation followed by palladium oxidation, intramolecular C(sp2)–H activation by a transient C(sp3)–Pd(IV) species, and selective carbon–carbon (C–C) bond-forming reductive

  苯并环丁烯 (BCB) 是有机合成、药物化学和材料科学中非常有价值的化合物。然而，从容易获得的起始材料催化模块化合成功能化 BCBs 仍然有限。我们在此报告了在N-氟苯磺酰亚胺 (NFSI)存在下通过 Pd(II) 催化的芳基硼酸和烯烃之间的形式 [2+2] 环化有效合成多种功能化的 BCB 。分子间碳钯化，然后是钯氧化，分子内 C(sp 2 )–H 由瞬态 C(sp 3)–Pd(IV) 物种，以及从高价五元钯环中选择性碳-碳 (C-C) 键形成还原消除来解释反应结果。烷基Pd(II) 到烷基Pd(IV) 物质的动力学有效氧化对于避免形成Heck 加合物很重要。该反应形成了环丁烯核心的两个 C-C 键，并与多种官能团相容。该转化不需要烯烃部分中的螯合双齿导向基团。,苯并环丁烯 (BCB) 是有机合成、药物化学和材料科学中非常有价值的化合物。然而，从容易获得的起始材料催化模块化合成功能化 BCBs
• SAVU P. M.; KATZENELLENBOGEN J. A., J. ORG. CHEM., 1981, 46, NO 2, 239-250
  作者：SAVU P. M.、 KATZENELLENBOGEN J. A.

  DOI：——

  日期：——