trans-5-(4-bromophenyl)-4-phenyldihydrofuran-2(3H)-one

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: trans-5-(4-bromophenyl)-4-phenyldihydrofuran-2(3H)-one
• 英文别名: (4R,5S)-5-(4-bromophenyl)-4-phenyloxolan-2-one
• 化学式: C₁₆H₁₃BrO₂
• 分子量: 317.182
• InChiKey: VDYQMFJKZQAQCI-GDBMZVCRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.19
• 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：

  trans-5-(4-bromophenyl)-4-phenyldihydrofuran-2(3H)-one 在 dimethyl sulfide borane 、 水 、 三乙胺 、 甘油 作用下， 以 二氯甲烷 为溶剂， 生成 Methanesulfonic acid (1S,2R)-1-(4-bromo-phenyl)-4-methanesulfonyloxy-2-phenyl-butyl ester
  参考文献：
  名称：

  Regio-, stereo-, and enantioselectivity in the electrophilic reactions of 2-amino-4-phenyl-3-butenenitriles

  摘要：

  The allylic anion generated from 2-(N-methylanilino)-4-phenyl-3-butenenitrile (1) reacted with iodomethane and 3-bromo-1-chloropropane in THF/HMPA to give the gamma-substitution products exclusively, predominantly in the 2Z-configuration. Substitution of the N-methylanilino group with the methyl ether of L-(-)-ephedrine resulted in the generation of chiral aminonitrile 2. Lithiated 2 reacted sluggishly in THF with allyl bromide and benzyl chloride in the absence of HMPA to give the gamma-substitution products predominantly in the 2Z-configuration, with little diastereoselectivity. The aminonitrile 3 prepared from cinnamaldehyde, L-(-)-ephedrine, and KCN was lithiated with 2 equiv of LDA resulting in high facial selectivity (76-100% diastereomeric excess) in alkylations in the presence of HMPA and LiI. Lithiated 3 reacted with propionaldehyde, benzaldehyde, and p-bromobenzaldehyde at-78-degrees-C to give the gamma-addition products, predominantly in the 4R-configuration (64-78% de). The stereochemistry of the isomers of each product was determined by chemical correlation and spectral methods including analyses of the CD spectra and X-ray diffraction. A bicyclic transition state C wherein lithium is chelated by both amino and alkoxy groups is proposed to interpret the observed stereoselectivity.

  DOI：

  10.1021/jo00059a027
• 作为产物：
  描述：

  (2Z,4R,5S)-5-hydroxy-2--4-phenyl-5-(4-bromophenyl)-2-pentenenitrile 在 草酸 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 生成 trans-5-(4-bromophenyl)-4-phenyldihydrofuran-2(3H)-one
  参考文献：
  名称：

  Regio-, stereo-, and enantioselectivity in the electrophilic reactions of 2-amino-4-phenyl-3-butenenitriles

  摘要：

  The allylic anion generated from 2-(N-methylanilino)-4-phenyl-3-butenenitrile (1) reacted with iodomethane and 3-bromo-1-chloropropane in THF/HMPA to give the gamma-substitution products exclusively, predominantly in the 2Z-configuration. Substitution of the N-methylanilino group with the methyl ether of L-(-)-ephedrine resulted in the generation of chiral aminonitrile 2. Lithiated 2 reacted sluggishly in THF with allyl bromide and benzyl chloride in the absence of HMPA to give the gamma-substitution products predominantly in the 2Z-configuration, with little diastereoselectivity. The aminonitrile 3 prepared from cinnamaldehyde, L-(-)-ephedrine, and KCN was lithiated with 2 equiv of LDA resulting in high facial selectivity (76-100% diastereomeric excess) in alkylations in the presence of HMPA and LiI. Lithiated 3 reacted with propionaldehyde, benzaldehyde, and p-bromobenzaldehyde at-78-degrees-C to give the gamma-addition products, predominantly in the 4R-configuration (64-78% de). The stereochemistry of the isomers of each product was determined by chemical correlation and spectral methods including analyses of the CD spectra and X-ray diffraction. A bicyclic transition state C wherein lithium is chelated by both amino and alkoxy groups is proposed to interpret the observed stereoselectivity.

  DOI：

  10.1021/jo00059a027

文献信息

• β,γ-trans-selective γ-butyrolactone formation via homoenolate cross-annulation of enals and aldehydes catalyzed by sterically hindered N-heterocyclic carbene
  作者：Ryuji Kyan、Yuya Kitagawa、Ryuji Ide、Kohei Sato、Nobuyuki Mase、Tetsuo Narumi

  DOI：10.1016/j.tet.2021.132191

  日期：2021.7

  Highly sterically hindered N-heterocyclic carbenes (NHCs), can be readily prepared from the corresponding anilines, and serve as organocatalysts in NHC-catalyzed homoenolate cross-annulation of α,β-enals and aryl aldehydes. This catalysis enables the convergent construction of β,γ-trans-disubstituted γ-butyrolactones that are an important class of molecules in synthetic and medicinal chemistry. The

  高度位阻 N-杂环卡宾 (NHC) 可以很容易地由相应的苯胺制备，并在 NHC 催化的 α,β-烯醛和芳基醛的均烯醇化物交叉环化中用作有机催化剂。这使得能够催化β的会聚结构，γ- TRAN S-γ二取代丁内酯是合成和药物化学分子的一类重要的。N-芳基取代基的空间特征有助于选择性，电子特征影响该反应的效率，该反应具有高非对映选择性，并以高达 91% 的产率提供各种 β,γ-二芳基-γ-丁内酯，高达1:99 博士
• N-Heterocyclic Carbene-Catalyzed Conjugate Umpolung for the Synthesis of γ-Butyrolactones
  作者：Frank Glorius、Christian Burstein、Serena Tschan、Xiulan Xie

  DOI：10.1055/s-2006-942447

  日期：——

  The N-heterocyclic carbene-catalyzed conjugate Umpolung of differently substituted α,β-unsaturated aldehydes, e. g. cinnamaldehydes, a-methylcinnamaldehydes, and crotonaldehydes, is described. Coupling of these compounds with a variety of electrophilic aldehydes and ketones results in the selective formation of highly substituted β- and γ-butyrolactones.

  描述了不同取代的α，β-不饱和醛，例如肉桂醛、α-甲基肉桂醛和巴豆醛的N-杂环卡宾催化的共轭Umpolung。这些化合物与各种亲电子醛和酮的偶联导致选​​择性形成高度取代的β-和γ-丁内酯。
• <i>N</i>-Heterocyclic Carbene-Catalyzed Generation of Homoenolates:  γ-Butyrolactones by Direct Annulations of Enals and Aldehydes
  作者：Stephanie S. Sohn、Evelyn L. Rosen、Jeffrey W. Bode

  DOI：10.1021/ja044714b

  日期：2004.11.1

  generation of reactive homoenolates from alpha,beta-unsaturated aldehydes. The catalyst-bound homoenolate reacts with electrophilic aldehydes leading, via the key intermediacy of an activated carboxylate, to gamma-butyrolactones in good yields and stereoselectivities. Importantly, this process demonstrates an unprecedented reaction mode for the generation of nucleophilic carbanions with a multifunctional

  由二芳基咪唑鎓盐原位制备的 N-杂环卡宾用作高效催化剂，用于从 α,β-不饱和醛生成反应性均烯醇化物。与催化剂结合的均烯醇化物与亲电子醛反应，通过活化羧酸盐的关键中间体，以良好的产率和立体选择性生成 γ-丁内酯。重要的是，该过程展示了一种前所未有的反应模式，用于在非常温和和方便的反应条件下使用多功能有机催化剂生成亲核碳负离子。
• Tuning the Catalyst Reactivity of Imidazolylidene Catalysts through Substituent Effects on the <i>N</i>-Aryl Groups
  作者：Ryuji Kyan、Kohei Sato、Nobuyuki Mase、Naoharu Watanabe、Tetsuo Narumi

  DOI：10.1021/acs.orglett.7b01105

  日期：2017.5.19

  Imidazolylidenes with 2,6-diethylphenyl groups were effective catalysts, and several mechanistic studies, including a deuterium kinetic isotope effect study, revealed that both steric and kinetic effects were responsible for the enhanced catalytic activity.

  合成了一系列具有各种N-芳基的咪唑鎓盐，并对其催化活性进行了评估，以研究N-芳基对通过3 →d 3-戊二醇合成γ-丁内酯的催化活性的贡献。添加。具有2,6-二乙基苯基基团的咪唑啉是有效的催化剂，包括氘代动力学同位素效应研究在内的一些机理研究表明，空间和动力学效应均是催化活性增强的原因。
• Imidazolium chiral ionic liquid derived carbene-catalyzed conjugate umpolung for synthesis of γ-butyrolactones
  作者：Feng-Li Yu、Jia-Jia Jiang、Dong-Mei Zhao、Cong-Xia Xie、Shi-Tao Yu

  DOI：10.1039/c3ra40211h

  日期：——

  A serial of imidazolium chiral ionic liquids starting from commercially available (−)-menthol as a chiral pool have been synthesized and successfully used for catalyzing conjugate umpolung of α,β-unsaturated aldehydes to stereoselectively synthesize γ-butyrolactones. The catalytic activities of these ionic liquids are examined and compared. The reaction of trans-cinnamaldehyde and p-methoxycarbonyl benzaldehyde as a model has been investigated in detail, and the reaction conditions have been optimized. Under the selected conditions, the ionic liquid catalyst can catalyze the annulations of trans-cinnamaldehyde with different aromatic aldehydes to afford differently substituted γ-butyrolactones. The recyclability of the ionic liquid catalyst is investigated, and the results have indicated that the catalyst can be recycled six times without obvious activity decreasing.

  一系列以市售的（−）-薄荷醇作为手性源的咪唑鎓型手性离子液体已被合成，并成功用于催化α,β-不饱和醛的共轭umpolung反应，以立体选择性地合成γ-丁内酯。考察并比较了这些离子液体的催化活性。以反式肉桂醛和对甲氧羰基苯甲醛的反应为模型进行了详细研究，并优化了反应条件。在选定的条件下，离子液体催化剂能够催化反式肉桂醛与不同芳香醛的环化反应，得到不同取代的γ-丁内酯。研究了离子液体催化剂的循环使用性能，结果表明该催化剂可循环使用六次而活性无明显下降。