(2R,5S,6R,7S)-2-tert-butyl-9-(dimethoxymethyl)-7-(methoxymethoxy)-6-[(E)-2-methyl-3-(2-trimethylsilylethoxymethoxy)prop-1-enyl]-1,3-dioxaspiro[4.5]dec-8-en-4-one | 198289-44-0

• 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: (2R,5S,6R,7S)-2-tert-butyl-9-(dimethoxymethyl)-7-(methoxymethoxy)-6-[(E)-2-methyl-3-(2-trimethylsilylethoxymethoxy)prop-1-enyl]-1,3-dioxaspiro[4.5]dec-8-en-4-one
• CAS: 198289-44-0
• 化学式: C₂₇H₄₈O₉Si
• 分子量: 544.758
• InChiKey: SRVUYDWVONDPRH-NJLYRCBFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  37
• 可旋转键数：
  15
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  90.9
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  (2R,5S,6R,7S)-2-tert-butyl-9-(dimethoxymethyl)-7-(methoxymethoxy)-6-[(E)-2-methyl-3-(2-trimethylsilylethoxymethoxy)prop-1-enyl]-1,3-dioxaspiro[4.5]dec-8-en-4-one 在 二异丁基氢化铝 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 1.0h， 以90%的产率得到(1S,5S,6R)-3-Dimethoxymethyl-1-hydroxymethyl-5-methoxymethoxy-6-[(E)-2-methyl-3-(2-trimethylsilanyl-ethoxymethoxy)-propenyl]-cyclohex-3-enol
  参考文献：
  名称：

  A Formal Total Synthesis of (+)-Tetronolide, the Aglycon of the Tetrocarcins:  Enantio- and Diastereoselective Syntheses of the Octahydronaphthalene (Bottom-Half) and Spirotetronate (Top-Half) Fragments

  摘要：

  A formal total synthesis of (+)-tetronolide, the aglycon of the tetrocarcins, has been achieved by virtue of the development of highly diastereo-and enantioselective syntheses of the bottom- and top-half fragments 4 and 5 reported herein. These fragments previously served as key intermediates in Yoshii's pioneering total synthesis of (+)-tetronolide, The synthesis of the bottom-half octahydronaphthalene unit 4 features the intramolecular Diels-Alder reaction of tetraenal 20 and proceeds in 17 steps and 5-6% yield from D-glyceraldehyde pentylidene acetal 8. The synthesis of the spirotetronate fragment 5 features the highly enantioselective exo selective Diels-Alder reaction of triene 37 and chiral dienophile 25b and proceeds in 14 steps and 10% overall yield from cis-2-butene-1,4-diol (38). An enantioselective synthesis of Boeckman's top-half cyclohexene fragment 6 sia the exo selective Diels-Alder reaction of diene 24 and dienophile 25a was also developed, but this route was deemed too inefficient for use in a projected total synthesis of the natural product. The syntheses of 5 and 6 provide important information on the utility of chiral dienophiles 25a and 25b in organic synthesis.

  DOI：

  10.1021/jo970960c
• 作为产物：
  描述：

  (E)-3-((2R,5S,6R,7S)-2-tert-Butyl-9-dimethoxymethyl-7-methoxymethoxy-4-oxo-1,3-dioxa-spiro[4.5]dec-8-en-6-yl)-2-methyl-acrylic acid methyl ester 在 L-Selectride 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 (2R,5S,6R,7S)-2-tert-butyl-9-(dimethoxymethyl)-7-(methoxymethoxy)-6-[(E)-2-methyl-3-(2-trimethylsilylethoxymethoxy)prop-1-enyl]-1,3-dioxaspiro[4.5]dec-8-en-4-one
  参考文献：
  名称：

  对苯二酚上半部分的对映选择性合成

  摘要：

  描述了对四氢萜内酯的上半螺形亚油酸酯亚基（3）的高度对映体和非对映体选择性合成。

  DOI：

  10.1016/s0040-4039(00)60939-5

文献信息

• Enantioselective synthesis of the top half of tetronolide
  作者：William R. Roush、Kazuo Koyama

  DOI：10.1016/s0040-4039(00)60939-5

  日期：1992.10

  A highly enantio- and diastereoselective synthesis of the top half spirotetronate subunit (3) of tetronolide is described.

  描述了对四氢萜内酯的上半螺形亚油酸酯亚基（3）的高度对映体和非对映体选择性合成。
• A Formal Total Synthesis of (+)-Tetronolide, the Aglycon of the Tetrocarcins:  Enantio- and Diastereoselective Syntheses of the Octahydronaphthalene (Bottom-Half) and Spirotetronate (Top-Half) Fragments
  作者：William R. Roush、Melissa L. Reilly、Kazuo Koyama、Bradley B. Brown

  DOI：10.1021/jo970960c

  日期：1997.12.1

  A formal total synthesis of (+)-tetronolide, the aglycon of the tetrocarcins, has been achieved by virtue of the development of highly diastereo-and enantioselective syntheses of the bottom- and top-half fragments 4 and 5 reported herein. These fragments previously served as key intermediates in Yoshii's pioneering total synthesis of (+)-tetronolide, The synthesis of the bottom-half octahydronaphthalene unit 4 features the intramolecular Diels-Alder reaction of tetraenal 20 and proceeds in 17 steps and 5-6% yield from D-glyceraldehyde pentylidene acetal 8. The synthesis of the spirotetronate fragment 5 features the highly enantioselective exo selective Diels-Alder reaction of triene 37 and chiral dienophile 25b and proceeds in 14 steps and 10% overall yield from cis-2-butene-1,4-diol (38). An enantioselective synthesis of Boeckman's top-half cyclohexene fragment 6 sia the exo selective Diels-Alder reaction of diene 24 and dienophile 25a was also developed, but this route was deemed too inefficient for use in a projected total synthesis of the natural product. The syntheses of 5 and 6 provide important information on the utility of chiral dienophiles 25a and 25b in organic synthesis.