(4R,5S)-4-benzyl-5-(hydroxymethyl)oxolan-2-one | 189758-63-2

• 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,5S)-4-benzyl-5-(hydroxymethyl)oxolan-2-one
• CAS: 189758-63-2
• 化学式: C₁₂H₁₄O₃
• 分子量: 206.241
• InChiKey: IFFWPGMSYFAUOY-GHMZBOCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  乙酸酐 、 (4R,5S)-4-benzyl-5-(hydroxymethyl)oxolan-2-one 在 高氯酸 作用下， 生成 [(2S,3R)-3-benzyl-5-oxooxolan-2-yl]methyl acetate
  参考文献：
  名称：

  Syn-Selective Michael Addition of Nitromethane Derivatives to Enoates Derived from (R)-(+)-Glyceraldehyde Acetonide

  摘要：

  We report the syn-selective Michael addition of a series of substituted primary and secondary nitromethane derivatives 4a-g to chiral enoates (Z)-2a and (E)-2a in the presence of TBAF . 3H(2)O or DBU. Regardless of the base employed, adducts syn-5a-g were obtained in good de (80-100%) from the reactions of 4a-g with (Z)-2a. However, in the addition to (E)-2a, the syn-diastereoselectivities depended on the structure of the nucleophile (80-90% de for nitromethane (4a), 80% de for phenylnitromethane (4g), 50 and 34% de for the primary nitromethane derivatives 4b and 4d, and 0 and 6% de for the secondary nitromethane derivatives 4e and 4f). A mixture of epimers (2:1/1:1) was obtained at the chiral center bearing the nitro group in 5b and 5d-g. The syn/anti ratio C-3,C-4 is kinetically controlled, while the epimeric ratio at the CNO2 chiral center (C-1') seems to be thermodynamically controlled. Adducts 5a,b,c,g were transformed into the respective cis-beta,gamma-disubstituted gamma-butyrolactones 6a, 7, 9a, and 9e. A mechanistic rationale to explain the observed diastereoselectivities is proposed.

  DOI：

  10.1021/jo960788x
• 作为产物：
  描述：

  ethyl (Z)-3-((S)-2,2-dimethyl-1,3-dioxolan-4-yl)acrylate 在 盐酸 、 sodium amalgam 、 正丁基锂 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 为溶剂， 反应 1.25h， 生成 (4R,5S)-4-benzyl-5-(hydroxymethyl)oxolan-2-one
  参考文献：
  名称：

  苯甲酰基苯磺酰基碳负离子与d-甘露糖醇衍生的立体选择性共轭加成反应

  摘要：

  共轭加成苄苯基磺酰基负碳离子（的2A ' - d '）从衍生enoates d - （+） -甘露糖醇（ë -或ž - 1A - C ^）用THF和THF / HMPA作为溶剂的研究。下动力学条件（-78℃），烯酸甲酯ë - 1A，B导致的混合物顺式- （- [R ，小号）和反- （小号，小号）加合物（55/45），以及顺式- （- [R ，小号）加合物是从烯醇酸酯获得的主要产物（〜90/10）Z - 1a。在热力学条件下（-78°C到室温），尽管受体中双键的几何形状也优先形成（-90/10 ）syn-（R，S）加合物。烯酸酯1C（Ë / Ž = 57/43），在α位置带有一个额外的苄基，也与负碳离子反应，2 ' ，A，B，热力学条件下，从而导致顺-adducts在良好的德（在三个控制新生成的立体成因中心）。将加合物定量转化为相应的β-γ-二取代的γ-丁内酯和α，β，γ-三取代的γ-丁内酯。这些内酯的1

  DOI：

  10.1021/jo035427d

文献信息

• Syn-Selective Michael Addition of Nitromethane Derivatives to Enoates Derived from (<i>R</i>)-(+)-Glyceraldehyde Acetonide
  作者：Jeronimo S. Costa、Ayres G. Dias、Aline L. Anholeto、Mônica D. Monteiro、Vera L. Patrocinio、Paulo R. R. Costa

  DOI：10.1021/jo960788x

  日期：1997.6.13

  We report the syn-selective Michael addition of a series of substituted primary and secondary nitromethane derivatives 4a-g to chiral enoates (Z)-2a and (E)-2a in the presence of TBAF . 3H(2)O or DBU. Regardless of the base employed, adducts syn-5a-g were obtained in good de (80-100%) from the reactions of 4a-g with (Z)-2a. However, in the addition to (E)-2a, the syn-diastereoselectivities depended on the structure of the nucleophile (80-90% de for nitromethane (4a), 80% de for phenylnitromethane (4g), 50 and 34% de for the primary nitromethane derivatives 4b and 4d, and 0 and 6% de for the secondary nitromethane derivatives 4e and 4f). A mixture of epimers (2:1/1:1) was obtained at the chiral center bearing the nitro group in 5b and 5d-g. The syn/anti ratio C-3,C-4 is kinetically controlled, while the epimeric ratio at the CNO2 chiral center (C-1') seems to be thermodynamically controlled. Adducts 5a,b,c,g were transformed into the respective cis-beta,gamma-disubstituted gamma-butyrolactones 6a, 7, 9a, and 9e. A mechanistic rationale to explain the observed diastereoselectivities is proposed.
• Stereoselective Conjugate Addition of Benzyl Phenylsulfonyl Carbanions to Enoates Derived from <scp>d</scp>-Mannitol
  作者：André R. G. Ferreira、Guilherme V. M. de A. Vilela、Mauro B. Amorim、Kátia P. Perry、Antônio J. R. da Silva、Ayres G. Dias、Paulo R. R. Costa

  DOI：10.1021/jo035427d

  日期：2004.6.1

  The conjugate addition of benzylic phenylsulfonyl carbanions (2a‘−d‘) to enoates derived from d-(+)-mannitol (E- or Z-1a−c) was studied using THF and THF/HMPA as solvent. Under kinetic conditions (−78 °C), enoate E-1a,b led to a mixture of syn-(R,S) and anti-(S,S) adducts (55/45), and syn-(R,S) adducts were the main product obtained (∼90/10) from enoate Z-1a. Under thermodynamic conditions (−78 °C

  共轭加成苄苯基磺酰基负碳离子（的2A ' - d '）从衍生enoates d - （+） -甘露糖醇（ë -或ž - 1A - C ^）用THF和THF / HMPA作为溶剂的研究。下动力学条件（-78℃），烯酸甲酯ë - 1A，B导致的混合物顺式- （- [R ，小号）和反- （小号，小号）加合物（55/45），以及顺式- （- [R ，小号）加合物是从烯醇酸酯获得的主要产物（〜90/10）Z - 1a。在热力学条件下（-78°C到室温），尽管受体中双键的几何形状也优先形成（-90/10 ）syn-（R，S）加合物。烯酸酯1C（Ë / Ž = 57/43），在α位置带有一个额外的苄基，也与负碳离子反应，2 ' ，A，B，热力学条件下，从而导致顺-adducts在良好的德（在三个控制新生成的立体成因中心）。将加合物定量转化为相应的β-γ-二取代的γ-丁内酯和α，β，γ-三取代的γ-丁内酯。这些内酯的1