3-deoxy-3-C-(ethoxycarbonyl)-methyl-1,2:5,6-di-O-propylidene-3-C-vinyl-α-D-allofuranose | 103516-15-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 3-deoxy-3-C-(ethoxycarbonyl)-methyl-1,2:5,6-di-O-propylidene-3-C-vinyl-α-D-allofuranose
• 英文别名: (2R,3R,4R,5S)-4-<(ethoxycarbonyl)methyl>-2,3-(isopropylidenedioxy)-5-<(1R)-1,2-(isopropylidenedioxy)ethyl>-4-vinyltetrahydrofuran；ethyl 2-[(3aR,5S,6R,6aR)-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-6-ethenyl-2,2-dimethyl-5,6a-dihydro-3aH-furo[2,3-d][1,3]dioxol-6-yl]acetate
• CAS: 103516-15-0
• 化学式: C₁₈H₂₈O₇
• 分子量: 356.416
• InChiKey: SCOJDGBCOMCDBA-YYZLIPTLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  72.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  3-deoxy-3-C-(ethoxycarbonyl)-methyl-1,2:5,6-di-O-propylidene-3-C-vinyl-α-D-allofuranose 在 palladium on activated charcoal 、 二异丁基氢化铝 、 溶剂黄146 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 、 水 为溶剂， 生成 (2R,3R,4R,5S)-2,3-(isopropylidenedioxy)-5-<(1R)-1,2-bis<(methylsulfonyl)oxy>ethyl>-4-methyl-4-vinyltetrahydrofuran
  参考文献：
  名称：

  通过邻苯二甲酸酯 CLAISEN 重排将 Gem-DILKYL 基团引入呋喃糖

  摘要：

  在 C-3 上具有烯丙醇官能团的 D-核糖或 L-lyxo-己呋喃糖衍生物的原酸酯克莱森重排立体选择性地进行，得到 3-C-二烷基化产物。产品新引入的四元​​中心的立体化学是通过化学修饰明确建立的。

  DOI：

  10.1246/cl.1985.1925
• 作为产物：
  描述：

  1,2:5,6-di-O-isopropylidene-α-D-glucofuranose 在 4 A molecular sieve 、 二异丁基氢化铝 、 丙酸 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 12.0h， 生成 3-deoxy-3-C-(ethoxycarbonyl)-methyl-1,2:5,6-di-O-propylidene-3-C-vinyl-α-D-allofuranose
  参考文献：
  名称：

  Ortho ester Claisen rearrangements of three 3-C-(hydroxymethyl)methylene derivatives of hexofuranose: stereoselective introduction of a quaternary center on C-3 of D-ribo-, L-lyxo-, and D-arabino-hexofuranoses

  摘要：

  DOI：

  10.1021/jo00383a005

文献信息

• INTRODUCTION OF<i>gem</i>-DILKYL GROUP TO HEXOFURANOSE BY ORTHO ESTER CLAISEN REARRANGEMENT
  作者：Kin-ichi Tadano、Yoko Idogaki、Hirohiko Yamada、Tetsuo Suami

  DOI：10.1246/cl.1985.1925

  日期：1985.12.5

  The ortho ester Claisen rearrangement of D-ribo- or L-lyxo- hexofuranose derivative which possesses an allyl alcohol functionality on C-3, proceeds stereoselectively to give a 3-C-dialkylated product. The stereochemistry of a newly introduced quaternary center of the product was unambiguously established by a chemical modification.

  在 C-3 上具有烯丙醇官能团的 D-核糖或 L-lyxo-己呋喃糖衍生物的原酸酯克莱森重排立体选择性地进行，得到 3-C-二烷基化产物。产品新引入的四元​​中心的立体化学是通过化学修饰明确建立的。
• Synthetic studies of viridenomycin. Construction of the cyclopentene carboxylic acid part
  作者：Jun Ishihara、Koji Hagihara、Hiroyuki Chiba、Kouichi Ito、Yumiko Yanagisawa、Kiichiro Totani、Kin-ichi Tadano

  DOI：10.1016/s0040-4039(00)00013-7

  日期：2000.3

  A highly functionalized cyclopentene carboxylic acid derivative, as an advanced synthetic intermediate of viridenomycin, was synthesized. The synthesis commenced with the previously reported highly functionalized tetrahydrofuran derivative prepared from d-glucose. The stereochemical confirmation of the present final compound was conducted by comparison with a compound synthesized very recently by the

  合成了高度功能化的环戊烯羧酸衍生物，作为viridenomycin的高级合成中间体。合成从先前报道的由d-葡萄糖制备的高度官能化的四氢呋喃衍生物开始。通过与Meyers小组最近合成的化合物进行比较，对本发明最终化合物进行了立体化学确认。
• Samarium(II) iodide-mediated reductive cyclization approach to total synthesis of the insect sex Attractant (−)-anastrephin
  作者：Kin-ichi Tadano、Yoshiaki Isshiki、Masaki Minami、Seiichiro Ogawa

  DOI：10.1016/s0040-4039(00)74773-3

  日期：1992.12

  C-substituted α,β-unsaturated ester 5 having a terminal aldehyde functionality, was effectively achieved using SmI2 in THF-HMPA. Starting with the major cyclization product 6, enantiospecific total synthesis of (−)-anastrephin. 1 was completed.

  在THF-HMPA中使用SmI 2有效地实现了对映体纯的γ，γ-差异C-取代的α，β-不饱和酯5的分子内还原环化，该酯具有末端醛官能团。从主要的环化产物6开始，（-）-anastrephin的对映体特异性全合成。1完成。
• Total syntheses of (-)-anastrephin, (-)-epianastrephin, and their 7a-epimers: use of samarium(II) iodide-mediated intramolecular reductive coupling for the construction of their hexahydrobenzofuran-2(3H)-one skeletons
  作者：Kinichi Tadano、Yoshiaki Isshiki、Masaki Minami、Seiichiro Ogawa

  DOI：10.1021/jo00075a021

  日期：1993.11

  D-Glucose-derived alpha,beta-unsaturated ester 17, which includes a geminally and differntially substituted gamma-carbon and a terminal aldehyde functionality, was subjected to a SMI2-Mediated intramolecular reductive coupling reaction in a THF solution containing 1/10 volume of HMPA. The reaction proceeded with moderate stereoselectivity to provide a diastereomeric mixture of hexahydrobenzofuran-2 (3H)-ones, in which cis-fused product 25 was obtained as the major isomer in 35% isolated yield. Two trans-fused coupling products 26 (17%) and 27 (14%) were also obtained. Starting from major product 25, the insect sex attractants (-)-anastrephin (1) and (-)-epianastrephin (2) were synthesized enantiospecifically. Two unnatural stereocongeners, (-)-7a-epi-anastrephin (3) and (-)-7a-epi-epianastrephin (4), were also derived from 25.
• Ortho ester Claisen rearrangements of three 3-C-(hydroxymethyl)methylene derivatives of hexofuranose: stereoselective introduction of a quaternary center on C-3 of D-ribo-, L-lyxo-, and D-arabino-hexofuranoses
  作者：Kinichi Tadano、Yoko Idogaki、Hirohiko Yamada、Tetsuo Suami

  DOI：10.1021/jo00383a005

  日期：1987.4