(2R)-methyl 2-methyl-2-(trans-styryl)acetate | 182699-64-5

• 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: (2R)-methyl 2-methyl-2-(trans-styryl)acetate
• 英文别名: methyl (R,E)-2-methyl-4-phenylbut-3-enoate；methyl (E,2R)-2-methyl-4-phenylbut-3-enoate
• CAS: 182699-64-5
• 化学式: C₁₂H₁₄O₂
• 分子量: 190.242
• InChiKey: KPZBEVBLJYUANV-AAXQSMANSA-N

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：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2R)-methyl 2-methyl-2-(trans-styryl)acetate 在 4-二甲氨基吡啶 、 lead 、 五氟苯基二苯基磷酸酯 、 碘 、 二异丁基氢化铝 、 N,N-二异丙基乙胺 、 间氯过氧苯甲酸 、 N,N'-二环己基碳二亚胺 、 锌 作用下， 以 乙醚 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 38.5h， 生成 2-{[{2-[(4-硝基苯基)磺酰]肼基<联氨基>}(羰基)乙酰基]氨基}苯甲酸
  参考文献：
  名称：

  Total Synthesis of Cryptophycins via a Chemoenzymatic Approach

  摘要：

  A highly convergent synthesis of cryptophycins in their enantiomerically-pure forms was achieved. Our strategy consists of the synthesis of the two units 3 and 4 and linking them together to form the macrocyclic ring. The upper unit 3 was prepared from 10 in four steps, and the lower unit 4 was prepared from 20 in three steps. Enantioselective biocatalytic methodology was used to prepare the requisite chiral building blocks, (R)-11 and (R)-19. The stereochemical versatility of this synthetic approach is demonstrated by the synthesis of cryptophycin A and the four diastereomers of cryptophycin C.

  DOI：

  10.1021/jo960972i
• 作为产物：
  描述：

  (E)-methyl 4-phenylbut-3-enoate 在 sodium azide 、 phosphate buffer 、 lithium diisopropyl amide 作用下， 以 水 为溶剂， 反应 120.42h， 生成 (2R)-methyl 2-methyl-2-(trans-styryl)acetate
  参考文献：
  名称：

  Total Synthesis of Cryptophycins via a Chemoenzymatic Approach

  摘要：

  A highly convergent synthesis of cryptophycins in their enantiomerically-pure forms was achieved. Our strategy consists of the synthesis of the two units 3 and 4 and linking them together to form the macrocyclic ring. The upper unit 3 was prepared from 10 in four steps, and the lower unit 4 was prepared from 20 in three steps. Enantioselective biocatalytic methodology was used to prepare the requisite chiral building blocks, (R)-11 and (R)-19. The stereochemical versatility of this synthetic approach is demonstrated by the synthesis of cryptophycin A and the four diastereomers of cryptophycin C.

  DOI：

  10.1021/jo960972i

文献信息

• Enantioselective Intermolecular Pd-Catalyzed Hydroalkylation of Acyclic 1,3-Dienes with Activated Pronucleophiles
  作者：Nathan J. Adamson、Katherine C. E. Wilbur、Steven J. Malcolmson

  DOI：10.1021/jacs.7b13300

  日期：2018.2.28

  We report a highly enantioselective Pd-PHOX-catalyzed intermolecular hydroalkylation of acyclic 1,3-dienes. Meldrum's acid derivatives and other activated C-pronucleophiles, such as β-diketones and malononitriles, react with a variety of aryl- and alkyl-substituted dienes in ≤20 h at room temperature. The coupled products, obtained in up to 96% yield and 97.5:2.5 er, are easily transformed into useful

  我们报道了一种高度对映选择性的 Pd-PHOX 催化的无环 1,3-二烯的分子间加氢烷基化反应。Meldrum 的酸衍生物和其他活化的 C-亲核试剂，例如 β-二酮和丙二腈，可在室温下 ≤20 小时内与各种芳基和烷基取代的二烯反应。偶联产物的产率高达 96%，比例为 97.5:2.5，很容易转化为下游合成有用的化学结构单元。
• Electrochemical Enantioselective Nucleophilic α-C(sp³)–H Alkenylation of 2-Acyl Imidazoles
  作者：Peng Xiong、Marcel Hemming、Sergei I. Ivlev、Eric Meggers

  DOI：10.1021/jacs.2c01686

  日期：2022.4.20

  catalytic asymmetric indirect electrolysis employing the combination of a redox mediator and a chiral-at-rhodium Lewis acid, which achieves a previously elusive enantioselective nucleophilic α-C(sp3)−H alkenylation of ketones. Specifically, 2-acyl imidazoles react with potassium alkenyl trifluoroborates in high yields (up to 94%) and with exceptional enantioselectivities (27 examples with ≥99% ee) without

  将电化学与不对称催化相结合，有望为构建非外消旋手性分子提供一种环境友好且有效的策略。然而，在实践中，手性催化剂在电极和溶液界面的电化学条件下的不稳定性或不相容性带来了重大挑战。在此，我们报道了一种催化不对称间接电解，采用氧化还原介体和手性铑路易斯酸的组合，实现了以前难以捉摸的对映选择性亲核α - C(sp 3 ) -酮的 H 烯基化。具体而言，2-酰基咪唑与链烯基三氟硼酸钾以高产率（高达 94%）和出色的对映选择性（27 个实例，≥99% ee）反应，无需任何额外的化学计量氧化剂（总共 40 个实例）。新的间接电合成可以缩放到克数量，并应用于天然产物隐藻素 A 和组织蛋白酶 K 抑制剂的中间体的直接合成。
• Highly Diastereoselective Michael Additions onto Dienyl Bis-Sulfoxides
  作者：Louis Fensterbank、Max Malacria、Franck Brebion、Jean Philippe Goddard

  DOI：10.1055/s-2005-872089

  日期：——

  cinnamaldehyde furnished bis-sulfoxide dienyl derivative 5, a remarkable 1,4-Michael acceptor that can lead in a highly dia­stereoselective manner to vinylcyclopropyl adducts. In a chelating mode of reactivity using a methylcopper reagent, a complete reversal of stereoselectivity is observed giving an enantiopure β,γ-unsaturated methyl ester intermediate that is used in the synthesis of cryptophycin

  报道了制备 (SS,SS)-双(对甲苯基亚磺酰基)甲烷 (4) 的优化程序。将 4 的锂盐缩合到肉桂醛上得到双亚砜二烯基衍生物 5，这是一种非凡的 1,4-迈克尔受体，可以以高度非对映选择性的方式生成乙烯基环丙基加合物。在使用甲基铜试剂的螯合反应模式中，观察到立体选择性的完全逆转，产生了用于合成隐藻素的对映体纯 β,γ-不饱和甲基酯中间体。
• Total Synthesis of Cryptophycins via a Chemoenzymatic Approach
  作者：Grzegorz M. Salamonczyk、Kang Han、Zhi-wei Guo、Charles J. Sih

  DOI：10.1021/jo960972i

  日期：1996.1.1

  A highly convergent synthesis of cryptophycins in their enantiomerically-pure forms was achieved. Our strategy consists of the synthesis of the two units 3 and 4 and linking them together to form the macrocyclic ring. The upper unit 3 was prepared from 10 in four steps, and the lower unit 4 was prepared from 20 in three steps. Enantioselective biocatalytic methodology was used to prepare the requisite chiral building blocks, (R)-11 and (R)-19. The stereochemical versatility of this synthetic approach is demonstrated by the synthesis of cryptophycin A and the four diastereomers of cryptophycin C.