(2RS,4RS,5RS)-2,5-diphenyl-4-ethoxycarbonyl-4-benzyl-1,3-dioxolane

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (2RS,4RS,5RS)-2,5-diphenyl-4-ethoxycarbonyl-4-benzyl-1,3-dioxolane
• 英文别名: ethyl (2R,4R,5R)-4-benzyl-2,5-diphenyl-1,3-dioxolane-4-carboxylate
• 化学式: C₂₅H₂₄O₄
• 分子量: 388.463
• InChiKey: ZNSAIWBXEGYIIW-VDKIKQQVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  29
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  苯丙酸,a-重氮基-,乙基酯 、 苯甲醛 在 dirhodium tetrakis(pivalate) 作用下， 以 二氯甲烷 为溶剂， 以55%的产率得到(2RS,4RS,5RS)-2,5-diphenyl-4-ethoxycarbonyl-4-benzyl-1,3-dioxolane
  参考文献：
  名称：

  Rh催化的α-烷基重氮酯形成二氧戊环：羰基叶立德的非对映选择性环加成反应，对β-氢化物的消除具有选择性

  摘要：

  本文描述了一种非对映选择性的Rh催化方法，用于从α-烷基-α-重氮酯制备二氧戊环。这代表了从具有β氢的α-重氮酯生成羰基化物的第一种通用方法，因为这类重氮化合物通常会通过β氢化物消除生成烯烃。随后与芳族醛的环加成反应得到具有异常高的非对映选择性的四取代的二氧戊环。提出了解释环加成的非对映选择性的模型。

  DOI：

  10.1021/jo702308f

文献信息

• Diastereoselective Synthesis of Tetrahydrofurans by Lewis Acid Catalyzed Intermolecular Carbenoid–Carbonyl Reaction–Cycloaddition Sequences: Unusual Diastereoselectivity of Lewis Acid Catalyzed Cycloadditions
  作者：Yuta Hashimoto、Kennosuke Itoh、Akikazu Kakehi、Motoo Shiro、Hiroyuki Suga

  DOI：10.1021/jo400858u

  日期：2013.6.21

  The effects of including metal salts for three. component reactions involving alpha-alkyl-alpha-diazo esters, aromatic aldehydes, and 3-(2-alkenoyl)-2-oxazolidinones are described, in terms of yields and diastereoselectivities. Metal tetrafluorborates (10-30 mol %) such as Co(BF4)(2)center dot 6H(2)O, Ni(BF4)(2)center dot 6H(2)O, and AgBF4 were effective in delivering high yields and diastereoselectivities (93:7 to 99:1) of the corresponding tetrahydrofuran derivatives while suppressing the competitive formation of 1,3-dioxolane. Using (S)-3-(2-alkenoyl)-4-isopropyl-2-oxazolidinones as the dipolarophiles in the three-component reactions, in the presence of Ni(BF4)(2)center dot 6H(2)O or Co(ClO4)(2)center dot 6H(2)O (10-30 mol %), optically active tetrahydrofurans that possess four successive asymmetric centers were synthesized in high diastereoselectivities (99:1). On the basis of the configuration of the cycloadduct using the X-ray analysis, the high diastereoselectivity could be explained by the unusual Re-face approach to the dipolarophile in the presence of the Lewis acid, proceeding through the s-cis conformer of the 3-(2-alkenoyl)-2-oxazolidinone with the two carbonyls in opposing directions (dipole-dipole interaction).
• Rh-Catalyzed Formation of Dioxolanes from α-Alkyl Diazoesters:  Diastereoselective Cycloadditions of Carbonyl Ylides with Selectivity over β-Hydride Elimination
  作者：Andrew DeAngelis、Patricia Panne、Glenn P. A. Yap、Joseph M. Fox

  DOI：10.1021/jo702308f

  日期：2008.2.1

  Described here is a diastereoselective Rh-catalyzed method for the preparation of dioxolanes from α-alkyl-α-diazoesters. This represents the first general method for generating carbonyl ylides from α-diazoesters that possess β-hydrogens, as such diazo compounds typically give rise to alkenes via β-hydride elimination. Subsequent cycloaddition with aromatic aldehydes gives tetrasubstituted dioxolanes

  本文描述了一种非对映选择性的Rh催化方法，用于从α-烷基-α-重氮酯制备二氧戊环。这代表了从具有β氢的α-重氮酯生成羰基化物的第一种通用方法，因为这类重氮化合物通常会通过β氢化物消除生成烯烃。随后与芳族醛的环加成反应得到具有异常高的非对映选择性的四取代的二氧戊环。提出了解释环加成的非对映选择性的模型。