(4R,5R,1'S)-2,2-dimethyl-4-(hydroxymethyl)-4-(methoxycarbonyl)-5-(1'-methylpropyl)-1,3-dioxolane | 144460-44-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 英文名称: (4R,5R,1'S)-2,2-dimethyl-4-(hydroxymethyl)-4-(methoxycarbonyl)-5-(1'-methylpropyl)-1,3-dioxolane
• 英文别名: methyl (4S,5R)-5-[(2S)-butan-2-yl]-4-(hydroxymethyl)-2,2-dimethyl-1,3-dioxolane-4-carboxylate
• CAS: 144460-44-6
• 化学式: C₁₂H₂₂O₅
• 分子量: 246.304
• InChiKey: IOGJREYZMJBMEH-SBMIAAHKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  65
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (4R,5R,1'S)-2,2-dimethyl-4-(hydroxymethyl)-4-(methoxycarbonyl)-5-(1'-methylpropyl)-1,3-dioxolane 在 4-二甲氨基吡啶 、 sodium chlorite 、 sodium dihydrogenphosphate 、 sodium amalgam 、 2-甲基-2-丁烯 、 草酰氯 、 四丁基氟化铵 、 溶剂黄146 、 二甲基亚砜 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 正己烷 、 二氯甲烷 、 水 、 乙酸乙酯 、 叔丁醇 为溶剂， 反应 60.83h， 生成 (E)-7-[(4S,5R)-5-[(2S)-butan-2-yl]-4-methoxycarbonyl-2,2-dimethyl-1,3-dioxolan-4-yl]-4-methylidenehept-6-enoic acid
  参考文献：
  名称：

  Total Synthesis and Stereochemistry of Alternaric Acid

  摘要：

  Determination of the stereochemistry and the total synthesis of alternaric acid 1 has been achieved. The stereostructure of 1 has been elucidated by stereoselective synthesis of four diastereoisomers of the C(9)-C(14) fragment 6, which had been obtained as a degradation product during structural studies. Key reactions of the total synthesis of 1 include the Julia olefination of tertiary aldehyde 6 and phenylsulfone 7 and novel one-pot construction of 3-acyl-4-hydroxy-5,6-dihydro-2-pyrone via Fries-type rearrangement of the O-enol acyl group of beta-keto-delta-valerolactone toward the a-position of the delta-lactone. The absolute configuration of alternaric acid has been shown to be that illustrated in structure 1. The modified Fries-type rearrangement method has also been extended to the synthesis of some other compounds containing a tricarbonylmethane structure.

  DOI：

  10.1021/jo00096a016
• 作为产物：
  描述：

  (4R,5R,1'S)-4-<<(tert-butyldiphenylsilyl)oxy>methyl>-4-(diethoxymethyl)-2,2-dimethyl-5-(1'-methylpropyl)-1,3-dioxolane 在 sodium chlorite 、 sodium dihydrogenphosphate 、 三甲基氯硅烷 、 四丁基氟化铵 、 双氧水 、 silica gel 、 溶剂黄146 作用下， 以 四氢呋喃 、 乙醚 、 丙酮 、 乙腈 为溶剂， 反应 12.0h， 生成 (4R,5R,1'S)-2,2-dimethyl-4-(hydroxymethyl)-4-(methoxycarbonyl)-5-(1'-methylpropyl)-1,3-dioxolane
  参考文献：
  名称：

  交替酸的立体化学; C（9）-C（14）片段的合成

  摘要：

  通过立体选择性合成C（9）-C（14）片段2的四个非对映异构体，已阐明了交替糖酸（1）的立体化学，C（9）-C（14）片段2是在结构研究期间作为降解产物获得的。

  DOI：

  10.1016/s0040-4039(00)61238-8

文献信息

• Stereochemistry of alternaric acid ; Synthesis of the C(9)-C(14) fragment
  作者：Hiroyasu Tabuchi、Akitami Ichihara

  DOI：10.1016/s0040-4039(00)61238-8

  日期：1992.8

  The stereochemistry of alternaric acid (1) has been elucidated by stereoselective synthesis of four diastereoisomers of C(9)-C(14) fragment 2, which had been obtained as degradation product during structural studies.

  通过立体选择性合成C（9）-C（14）片段2的四个非对映异构体，已阐明了交替糖酸（1）的立体化学，C（9）-C（14）片段2是在结构研究期间作为降解产物获得的。
• Total Synthesis and Stereochemistry of Alternaric Acid
  作者：Hiroyasu Tabuchi、Taisuke Hamamoto、Shokyo Miki、Tsuyoshi Tejima、Akitami Ichihara

  DOI：10.1021/jo00096a016

  日期：1994.8

  Determination of the stereochemistry and the total synthesis of alternaric acid 1 has been achieved. The stereostructure of 1 has been elucidated by stereoselective synthesis of four diastereoisomers of the C(9)-C(14) fragment 6, which had been obtained as a degradation product during structural studies. Key reactions of the total synthesis of 1 include the Julia olefination of tertiary aldehyde 6 and phenylsulfone 7 and novel one-pot construction of 3-acyl-4-hydroxy-5,6-dihydro-2-pyrone via Fries-type rearrangement of the O-enol acyl group of beta-keto-delta-valerolactone toward the a-position of the delta-lactone. The absolute configuration of alternaric acid has been shown to be that illustrated in structure 1. The modified Fries-type rearrangement method has also been extended to the synthesis of some other compounds containing a tricarbonylmethane structure.