(1R,2S,2'R,4R)-2'-(tert-butyl)spiro[bicyclo[2.2.1]heptane-2,4'-[1,3]dioxolan]-5-en-5'-one | 140850-09-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧戊环
• 英文名称: (1R,2S,2'R,4R)-2'-(tert-butyl)spiro[bicyclo[2.2.1]heptane-2,4'-[1,3]dioxolan]-5-en-5'-one
• 英文别名: (1R,2R,2'R,4R)-2'-(tert-butyl)spiro[bicyclo[2.2.1]heptane-2,4'-[1,3]dioxolan]-5-en-5'-one；(1S,2R,2'S,4S)-2'-(tert-butyl)spiro[bicyclo[2.2.1]heptane-2,4'-[1,3]dioxolan]-5-en-5'-one；(1R,2R,2'S,4R)-2'-(tert-butyl)spiro[bicyclo[2.2.1]heptane-2,4'-[1,3]dioxolan]-5-en-5'-one；(1S,2S,2'S,4S)-2'-(tert-butyl)spiro[bicyclo[2.2.1]heptane-2,4'-[1,3]dioxolan]-5-en-5'-one；(1S,2S,2'R,4S)-2'-(tert-butyl)spiro[bicyclo[2.2.1]heptane-2,4'-[1,3]dioxolan]-5-en-5'-one
• CAS: 140850-09-5；116635-38-2；116697-42-8；116697-43-9；128707-81-3；128707-82-4；140850-06-2；140850-10-8
• 化学式: C₁₃H₁₈O₃
• 分子量: 222.284
• InChiKey: FYQOJIXQLOGAAT-KOVQTIFSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.27
• 重原子数：
  16.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (1R,2S,2'R,4R)-2'-(tert-butyl)spiro[bicyclo[2.2.1]heptane-2,4'-[1,3]dioxolan]-5-en-5'-one 在 过氧乙酸 、 sodium carbonate 、 溶剂黄146 作用下， 以 二氯甲烷 为溶剂， 以26 %的产率得到(2S,5R,1'R,2'R,4'R,5'R)-spiro[2-t-butyl-1,3-dioxolan-4-one-5,6'-3'-oxatricyclo[3.2.1.0^2.4]octane]
  参考文献：
  名称：

  手性 1,3-Dioxolan-4-Ones 的新化学

  摘要：

  (2S,5S)-5-Phenyl-2-t-butyl-1,3-dioxolan-4-one，很容易衍生自扁桃酸，经过迈克尔加成到具有绝对构型的丁烯内酯和 4-甲氧基-β-硝基苯乙烯在每种情况下通过 X 射线衍射确认的产物。在前一种情况下，热裂解得到苯基酮，从而说明二氧戊环用作手性苯甲酰基阴离子等价物。(2S)-5-methylene-2-t-butyl-1,3-dioxolan-4-one 的 Diels-Alder 环加成化学，衍生自乳酸，已通过确定的四种加合物的 X 射线结构进行了进一步研究. 在一种情况下，加合物的热裂解产生手性环氧酮，由二氧戊环作为手性乙烯酮等价物产生，而在其他情况下，产物可以深入了解二氧戊环裂解过程的机制。

  DOI：

  10.3390/molecules28093845
• 作为产物：
  描述：

  (2SR,5S)-2-tert-butyl-5-<(phenylthio)methyl>-1,3-dioxolan-4-one 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 33.0h， 生成 (1R,2S,2'R,4R)-2'-(tert-butyl)spiro[bicyclo[2.2.1]heptane-2,4'-[1,3]dioxolan]-5-en-5'-one
  参考文献：
  名称：

  Enantioselective synthesis of 2-alkyl-5-methylene-1,3-dioxolan-4-ones and exo-selective Diels-Alder reactions with cyclopentadiene

  摘要：

  Highly stereoselective syntheses of chiral dienophiles (R)-1 and (R)-2 are described. Diazotization of L-serine in the presence of HCI and then treatment of the resulting beta-hydroxy-alpha-chloropropionic acid (S)-7 with KOH provides potassium glycidate ((R)-8) in good yield and high enantiomeric purity. Treatment of (R)-8 with PhSH in MeOH then provides alpha-hydroxy acid (S)-10 that can be purified by recrystallization. Condensation of (S)-10 with either pivalaldehyde or cyclohexanecarboxaldehyde followed by oxidation to the sulfone and DBU-promoted elimination of benzenesulfinic acid then provides dienophiles (R)-1 and (R)-2, respectively. Highly exo-selective Diels-Alder reactions of (R)-1 and (R)-2 with cyclopentadiene are also described. The major cycloadduct (-)-15 (94% of total) from the Diels-Alder reaction of 1 was shown to have an enantiomeric purity of greater-than-or-equal-to 99% ee. This figure defines the lower limit of enantiomeric purity of (R)-1. The diastereofacial selectivity of the Diels-Alder reactions of 1 in the exo manifold (50:1) is greater than that of 2 (20:1), as would be expected on the basis of the different steric requirements of the tert-butyl and cyclohexyl substituents of the two reagents. Consequently, dienophile 1 is the preferred reagent for complex synthetic applications, either as a chiral ketene equivalent or in contexts in which the a-hydroxy acid functionality will be preserved in the ultimate synthetic target. Finally, the possible role of dipole effects on the exo selectivity of the Diels-Alder reactions of these and related dienophiles are briefly discussed.

  DOI：

  10.1021/jo00038a028

文献信息

• Synthesis and Diels-Alder reactions of 2-alkyl-5-methylene-1,3-dioxolan-4-ones and 2-alkyl-3-acyl-5-methylene-1,3-oxazolidin-4-ones: Highly exo and diastereoface selective chiral ketene equivalents
  作者：William R. Roush、Amy P. Essenfeld、Joseph S. Warmus、Bradley B. Brown

  DOI：10.1016/s0040-4039(00)70683-6

  日期：1989.1

  Chiral dienophiles 1–3 undergo highly exo and diastereoface selective Diels-Alder reactions. The Diels-Alder reactions of 3 are also highly exo selective under Lewis acid catalyzed conditions.

  手性亲双烯体1-3发生高度exo和非对映体选择性Diels-Alder反应。的狄尔斯-阿尔德反应3也路易斯酸催化条件下是高度选择性的外型。
• Mattay, Jochen; Mertes, Juergen; Maas, Gerhard, Chemische Berichte, 1989, vol. 122, p. 327 - 330
  作者：Mattay, Jochen、Mertes, Juergen、Maas, Gerhard

  DOI：——

  日期：——