(4R,5R)-5-(4-bromophenyl)-4-phenyltetrahydrofuran-2-one | 147471-40-7

• 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: (4R,5R)-5-(4-bromophenyl)-4-phenyltetrahydrofuran-2-one
• 英文别名: cis-5-(4-bromophenyl)-4-phenyldihydrofuran-2(3H)-one；(4R,5R)-5-(4-bromophenyl)-4-phenyloxolan-2-one
• CAS: 147471-40-7
• 化学式: C₁₆H₁₃BrO₂
• 分子量: 317.182
• InChiKey: VDYQMFJKZQAQCI-ZBFHGGJFSA-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：

  (4R,5R)-5-(4-bromophenyl)-4-phenyltetrahydrofuran-2-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 (1R,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,5R)-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 (4R,5R)-5-(4-bromophenyl)-4-phenyltetrahydrofuran-2-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

• 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。
• Bifunctional N‐Heterocylic Carbene‐Catalyzed Highly Enantioselective Trans‐Cyclopentannulation of Enals and Enones via Homoenolate
  作者：Zhiwei Jiang、Martial Toffano、Giang Vo‐Thanh、Chloée Bournaud

  DOI：10.1002/cctc.202001513

  日期：2021.1.20

  An efficient and flexible synthesis of a new class of chiral bifunctional NHC catalyst has been reported. These new imidazolylidene NHCs, bearing a (thio)urea function as a hydrogen bond donor promoted efficiently highly diastereoselective trans‐cyclopentannulation of enals and enones in moderate to good yields (up to 69 % yield) along with excellent enantioselectivity (up to 96 % ee). This methodology

  已经报道了新型的手性双官能NHC催化剂的有效和灵活的合成。这些具有（硫）脲作为氢键供体的新型咪唑基NHCs以中等至良好的收率（高达69％的收率）和出色的对映选择性（ee高达96％）高效地促进了烯类和烯酮的高非对映选择性反式环戊烯环化）。该方法可以应用于各种各样的基板（30个示例）。
• Chemoselective Umpolung of Enals for Asymmetric Homoenolate Cross-Annulation of Enals and Aldehydes Catalyzed by N-Heterocyclic Carbene
  作者：Ryuji Ide、Ryuji Kyan、Thien Phuc Le、Yuya Kitagawa、Kohei Sato、Nobuyuki Mase、Tetsuo Narumi

  DOI：10.1021/acs.orglett.9b03509

  日期：2019.11.15

  An asymmetric homoenolate cross-annulation of enals and aldehydes with high enantioselectivity is realized by NHC-catalyzed chemoselective umpolung of enals. The reaction proceeds in a highly chemoselective manner, selectively generating the conjugated Breslow intermediates from enals rather than aldehydes, enabling the homoenolate addition of enals to aldehydes in preference to competing acyl anion-mediated

  通过NHC催化的化学对映体的化学选择，实现了对映体和醛类的不对称均烯酸酯交叉环化，具有很高的对映体选择性。该反应以高度化学选择性的方式进行，从烯醛而不是醛选择性地产生共轭的Breslow中间体，从而使烯醛均烯酸酯加成到醛中，而不是竞争性的阴离子阴离子介导的反应。以高收率和高对映选择性形成富含对映体的取代γ-丁内酯。
• 10.1021/acs.joc.4c01045
  作者：Kunitomo, Noritaka、Kano, Taichi

  DOI：10.1021/acs.joc.4c01045

  日期：——

  The Cu-catalyzed asymmetric conjugate addition of arylboronic acids to enone diesters is reported. This operationally simple and scalable reaction proceeded under mild conditions. The practical utility of this approach was demonstrated by the synthesis of structurally important γ-lactones and a cyclopentene that bear an aryl group. Mechanistic studies revealed that two different copper catalytic species

  报道了铜催化芳基硼酸与烯酮二酯的不对称共轭加成。这种操作简单且可扩展的反应在温和条件下进行。该方法的实用性通过结构上重要的γ-内酯和带有芳基的环戊烯的合成得到了证明。机理研究表明，两种不同的铜催化物质在反应中协同作用。
• Chang Chih-Jung, Fang Jim-Min, Liao Li-Fan, J. Org. Chem., 58 (1993) N 7, S 1754-1761
  作者：Chang Chih-Jung, Fang Jim-Min, Liao Li-Fan

  DOI：——

  日期：——