5-benzyl-2,2-dimethyl-5-phenyl-1,3-dioxolan-4-one | 136962-24-8

• 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: 5-benzyl-2,2-dimethyl-5-phenyl-1,3-dioxolan-4-one
• CAS: 136962-24-8
• 化学式: C₁₈H₁₈O₃
• 分子量: 282.339
• InChiKey: HBHJFTUGYZNBBR-UHFFFAOYSA-N

物化性质

• 熔点：
  47-49 °C(Solv: dichloromethane (75-09-2))
• 沸点：
  414.4±33.0 °C(Predicted)
• 密度：
  1.144±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  5-benzyl-2,2-dimethyl-5-phenyl-1,3-dioxolan-4-one 600.0 ℃ 、1.33 Pa 条件下， 以97%的产率得到二苯基乙酮
  参考文献：
  名称：

  Behaviour of Dioxolanones as Chiral Acyl Anion Equivalents

  摘要：

  1,3-二恶烯-4-酮可以方便地从α-羟基酸中得到，通过去质子化-烷基化后进行快速真空热解，作为方便的酰基阴离子等效物。它们的阴离子与乙基克罗顿酸酯的共轭加成类似可得到β-甲基-γ-氧基酯，使用手性二恶烯酮可以达到最高86%的对映体过量。

  DOI：

  10.1055/s-1998-1569
• 作为产物：
  描述：

  扁桃酸 在 氢气 、 lithium diisopropyl amide 作用下， 生成 5-benzyl-2,2-dimethyl-5-phenyl-1,3-dioxolan-4-one
  参考文献：
  名称：

  Behaviour of Dioxolanones as Chiral Acyl Anion Equivalents

  摘要：

  1,3-二恶烯-4-酮可以方便地从α-羟基酸中得到，通过去质子化-烷基化后进行快速真空热解，作为方便的酰基阴离子等效物。它们的阴离子与乙基克罗顿酸酯的共轭加成类似可得到β-甲基-γ-氧基酯，使用手性二恶烯酮可以达到最高86%的对映体过量。

  DOI：

  10.1055/s-1998-1569

文献信息

• Nucleophilic Benzoylation Using a Mandelic Acid Dioxolanone as a Synthetic Equivalent of the Benzoyl Carbanion. Oxidative Decarboxylation of α-Hydroxyacids
  作者：Gonzalo Blay、Isabel Fernández、Belén Monje、José Pedro

  DOI：10.3390/90500365

  日期：——

  The synthesis of alkyl aryl ketones using a mandelic acid dioxolanone as a synthetic equivalent (Umpolung) of the benzoyl carbanion is reported. The methodology involves alkylation of the mandelic acid dioxolanone, hydrolysis of the dioxolanone moiety in the alkylated products and oxidative decarboxylation of the resulting alpha-hydroxyacids. The last step is carried out in a catalytic aerobic way

  报道了使用扁桃酸二氧戊环酮作为苯甲酰基碳负离子的合成等价物 (Umpolung) 合成烷基芳基酮。该方法涉及扁桃酸二氧戊环酮的烷基化、烷基化产物中二氧戊环酮部分的水解和所得α-羟基酸的氧化脱羧。最后一步是在非常温和的条件下，在新戊醛存在下，使用 Co (III) 配合物以催化有氧方式进行的。
• PLE catalyzed hydrolyses of α-substituted α-hydroxy esters: The influence of the substituents.
  作者：Henk Moorlag、Richard M. Kellogg

  DOI：10.1016/s0957-4166(00)86125-x

  日期：1991.1

  The enzymatic hydrolyses of a variety of α-substituted mandelic and lactic esters using pig liver esterase (PLE) have been investigated. High to moderate enantioselectivity was found for various α-substituted mandelic esters, whereas PLE showed low to no enantioselectivity for α-substituted lactic esters. We observed that the enantioselectivity of PLE depends strongly on the length and nature of the

  已经研究了使用猪肝酯酶（PLE）酶促水解各种α-取代的扁桃酸酯和乳酸酯的方法。发现对各种α-取代的扁桃酸酯具有高到中等的对映选择性，而PLE对α-取代的乳酸酯显示出低至没有对映选择性。我们观察到，PLE的对映选择性很大程度上取决于α位置取代基的长度和性质。讨论了PLE的活动站点模型的一些后果。
• Lipase AKG mediated resolutions of α,α-disubstituted 1,2-diols in organic solvents; remarkably high regio- and enantio-selectivity
  作者：Robert P. Hof、Richard M. Kellogg

  DOI：10.1039/p19960002051

  日期：——

  Diols 1, which contain adjacent tertiary and primary hydroxy groups, can be selectively mono-acylated at the primary hydroxy group by many lipases in organic solvents, Since the reaction does not take place at the chiral tertiary centre itself, observed enantioselectivities are usually low. Only the combination of one lipase, lipase AKG (Amano, Pseudomonas sp.), with selected substrates gives high enantioselectivities (E 20 to > 200), Also, the solvent and acyl donor employed influences the outcome, On the basis of the results of Lipase AKG towards substrates 1 an active site model for this specific lipase has been developed, which can account for the results obtained, Fu!! experimental details on the synthesis of diols 1 and enzymatic preparation of acetates 2 are given, Also, the absolute stereochemistry of the enzymatically prepared diols 1 has been established by independent synthesis from (R)-mandelic acid.

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