(2R)-2-cyclohexyl-5-methylene-1,3-dioxolan-4-one | 140850-05-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物
• 英文名称: (2R)-2-cyclohexyl-5-methylene-1,3-dioxolan-4-one
• 英文别名: (2R)-2-cyclohexyl-5-methylidene-1,3-dioxolan-4-one
• CAS: 140850-05-1
• 化学式: C₁₀H₁₄O₃
• 分子量: 182.219
• InChiKey: OCVMIMVUZXOECW-SNVBAGLBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.7
• 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：

  ethyl 6-<<(tert-butyldiphenylsilyl)oxy>methyl>-2-methyl-2(E),4(E),6(Z)-octatrienoate 、 (2R)-2-cyclohexyl-5-methylene-1,3-dioxolan-4-one 以73%的产率得到
  参考文献：
  名称：

  ROUSH, WILLIAM R.;BROWN, BRADLEY B., TETRAHEDRON LETT., 30,(1989) N2, C. 7309-7312

  摘要：

  DOI：
• 作为产物：
  描述：

  (2R,5S)-2-cyclohexyl-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 为溶剂， 反应 18.0h， 生成 (2R)-2-cyclohexyl-5-methylene-1,3-dioxolan-4-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

• A highly diastereo- and enantioselective synthesis of the top half of kijanolide
  作者：William R. Roush、Bradley B. Brown

  DOI：10.1021/jo00060a035

  日期：1993.4

  A highly diastereo- and enantioselective synthesis of spirotetronate 4 corresponding to the top half of kijanolide is reported. This synthesis features the novel exo-selective Diels-Alder reaction of triene 6 and the chiral, nonracemic dienophiles (R)-7 and (R)-8. The reaction of 6 and (R)-7 produced a mixture of the desired exo cycloadduct 28, the unexpected exo diastereofacial isomer 29, and a minor amount of the endo cycloadduct 30. However, the Diels-Alder reaction of 6 and dienophile (R)-8 with the more sterically demanding tert-butyl substituent provided a 13-14:1 mixture of exo cycloadduct 38 and endo isomer 39; the exo diastereofacial isomer corresponding to 29 was not observed. Elaboration of 28 and 38 to spirotetronate 4 proceeded by way of the Dieckmann cyclization of alpha-acetoxy ester 5.