(4R,5R)-(-)-4,5-dihydro-5-ethyl-4-phenyl-(3H)-furan-2-one | 147599-27-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (4R,5R)-(-)-4,5-dihydro-5-ethyl-4-phenyl-(3H)-furan-2-one
• 英文别名: (4R,5R)-5-ethyl-4-phenyloxolan-2-one
• CAS: 147599-27-7
• 化学式: C₁₂H₁₄O₂
• 分子量: 190.242
• InChiKey: UTARBSOFHVYSAF-GHMZBOCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 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)-(-)-4,5-dihydro-5-ethyl-4-phenyl-(3H)-furan-2-one 在 dimethyl sulfide borane 、 水 、 甘油 作用下， 生成 (3R,4R)-3-Phenyl-hexane-1,4-diol
  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：

  2--4-phenyl-3-butenenitrile 在 草酸 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 13.0h， 生成 (4R,5R)-(-)-4,5-dihydro-5-ethyl-4-phenyl-(3H)-furan-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

• Synthesis of versatile chiral intermediates by enantioselective conjugate addition of alkenyl Grignard reagents to enamides deriving from (R)-(−)- or (S)-(+)-2-aminobutan-1-ol
  作者：Eric Brown、Christelle Deroye、Joël Touet

  DOI：10.1016/s0957-4166(98)00135-9

  日期：1998.5

  Conjugate addition of but-3-enylmagnesium bromide to the chiral crotonamide (R)-(+)- and (S)-(−)-3, followed by hydrolysis and oxidation, afforded enantiopure (R)-(+)- and (S)-(−)-3-methyladipic acids 8, respectively. Conjugate addition of vinylmagnesium chloride to the chiral crotonamide and cinnamamides (R)-(+)-3–5, followed by hydrolysis, gave the alkenoic acids (S)-12–14, respectively. Iodolactonization

  在手性巴豆酰胺（R）-（+）-和（S）-（-）- 3上共加入溴3-丁基溴化镁，然后水解和氧化，得到对映纯（R）-（+）-和（S）-（-）- 3-甲基己二酸8。共轭加成的乙烯基氯化镁的手性巴豆酰胺和cinnamamides（[R ）- （+） - 3 - 5，接着进行水解，得到的链烯酸（小号） - 12 - 14，分别。后者的碘内酯化导致生成5-碘甲基内酯（+）- 15 – 17，将其借助于减少Ñ -Bu 3 SNH入反式二取代的5- methyllactones（+） - 19 - 21，分别。用LiMe 2 Cu或n- Bu 2 CuLi处理碘甲基内酯（+）- 16，得到了反式-5-烷基-4-苯基内酯（-）- 22或（+）- 23。
• Stereoconvergent Conjugate Addition of Arylboronic Acids to α-Angelica Lactone Derivatives: Synthesis of Stereochemically Complex γ-Butyrolactones
  作者：Jessica A. Griswold、Jeffrey S. Johnson

  DOI：10.1021/acscatal.9b04405

  日期：2019.12.6

  with up to three contiguous stereocenters. The reaction proceeds under a dynamic kinetic resolution manifold by isomerizing the achiral starting material into an interconverting mixture of enantiomeric conjugate acceptors, followed by catalyst-controlled, enantiomer-selective 1,4-addition. Base-promoted racemization of the intermediate α,β-butenolide is possible due to the high kinetic and thermodynamic

  催化的不饱和羰基立体聚合1,4-加成反应很少见，但具有很高的潜在价值。这封信详细介绍了硼酸和β，γ-丁烯醇内酯的对映选择性芳基化反应的进展。这些反应由可商购的羟基[（S）-BINAP]-铑（I）二聚体，得到立体化学复杂的γ-丁内酯衍生物。反应产物提供适于进一步操纵的功能，并且可以导致产物具有多达三个连续的立体中心。通过将非手性原料异构化为对映体共轭受体的相互转化混合物，然后在催化剂控制的对映体选择性1,4-加成中，反应在动态动力学拆分歧管上进行。由于γ-质子的高动力学和热力学酸性，中间体α，β-丁烯内酯的碱促进外消旋作用是可能的。
• 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：——