epi-botryodiplodin | 113531-94-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: epi-botryodiplodin
• 英文别名: Epibotryodiplodin；(2S,3S)-3-hydroxymethyl-2-methyl-4-oxo-pentanal (Ξ)-1->3-cyclohemiacetal；1-((3S)-5ξ-hydroxy-4t-methyl-tetrahydro-furan-3r-yl)-ethanone；(1Ξ)-L-erythro-botryodiplodin；1-[(3S,4S)-5-hydroxy-4-methyloxolan-3-yl]ethanone
• CAS: 113531-94-5
• 化学式: C₇H₁₂O₃
• 分子量: 144.17
• InChiKey: CLYSZQBIUYRLNX-KGYJPBEYSA-N

物化性质

• 沸点：
  249.4±40.0 °C(Predicted)
• 密度：
  1.126±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  (3S,4S)-(-)-4-acetyl-3-methyl-2(3H)-dihydrofuranone 在 silver(I) nitrite 、 碘 、 zinc trifluoromethanesulfonate 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 10.0h， 生成 epi-botryodiplodin
  参考文献：
  名称：

  A combined experimental and computational strategy in the assignment of absolute configurations of 4-methyl-5-oxo-tetrahydrofuran-3-carboxylic acids and their esters

  摘要：

  Enantiopure cis- and trans-4-methylparaconic acids and their alkyl esters were synthesized by a procedure involving the kinetic enzymatic resolution of diastereomeric lactonic esters. Thus, ethyl cis- and trans-4-methyl-5-oxo-tetrahydrofuran-3-carboxylates were isolated, at high conversion values, with 99% ee from the hydrolyses with HLAP and alpha-CT, respectively. The corresponding enantiopure cis- and trans-lactonic acids were also obtained. The absolute configurations of the products were assigned by chemical correlation, by analysis of their circular dichroism spectra and by electronic structure calculations. All three methodologies lead to the same assignment for the species considered, another example of successful interplay between experiment and theory. (C) 2005 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tetasy.2005.08.018

文献信息

• Organocatalytic Michael addition, a convenient tool in total synthesis. First asymmetric synthesis of (−)-botryodiplodin
  作者：Olivier Andrey、Annick Vidonne、Alexandre Alexakis

  DOI：10.1016/j.tetlet.2003.09.017

  日期：2003.10

  The asymmetric Michael addition of propionaldehyde to (2E)-(3-nitro-but-2-enyloxymethyl)-benzene 8, catalyzed by the chiral diamine (S,S)-N-iPr-2,2′-bipyrrolidine, afforded, with 93% ee, a precursor 9 of (−)-botryodiplodin. The nitro functionality of 9 was converted to a ketone via a Nef reaction to give, after a few steps, the enantiomerically enriched (−)-botryodiplodin.

  丙醛在手性二胺（S，S）-N - i Pr-2,2'-联吡咯烷的催化下，丙醛向（2 E）-（3-硝基-丁-2-烯氧基甲基）-苯8的不对称迈克尔加成，获得了93％ee的（-）-botryodiplodin的前体9。经由Nef反应将9的硝基官能团转化为酮，从而在几步后得到对映体富集的（-）-botododiplodin。
• Diastereoselective conjugate addition of lithium methylcyanocuprate to the chiral isoprene units 2-(R)- and (S)-benzyloxy-2,5-dihydro-4-furancarbox-aldehyde. Total synthesis of (−)- and (+)-botryodiplodin and (+)- and (−)-epibotryodiplodin.
  作者：Nicola Rehnberg、Torbjörn Frejd、Göran Magnusson

  DOI：10.1016/s0040-4039(00)95543-6

  日期：1987.1

  Conjugate addition of lithium methylcyanocuprate to the titlealdehydes proceeded with high diastereoselectivity (d.e. 94%). Methyl lithium 1,2-addition, followed by Swern oxidation of the resultingalcohols, gave benzyl botryodiplodin and benzyl epi-botryodiplodin.Hydrogenolysis of the benzyl groups gave the enantiomeric pairs ofbotryodiplodin 10r and 10s and epi-botryodiplodin (9r and 9s).

  将甲基氰基丙酸锂共轭加到标题醛中，具有很高的非对映选择性（de 94％）。加入1,2-甲基锂锂，然后对得到的醇进行Swern氧化，得到苄基葡萄球菌双磷酸酯和苄基表柔和的双宝洛丁。对苄基进行加氢解得到了对映体对的botododiplodin 10r和10s和epi-botryodiplodin（9r和9s）。
• Allenyl ethers as precursors of .alpha.-methylene-.gamma.-butyrolactones and botryodiplodin derivatives
  作者：Jean Pierre Dulcere、Mohamed Naceur Mihoubi、Jean Rodriguez

  DOI：10.1021/jo00073a033

  日期：1993.10

  Beta-Bromopropargyl ethers 2a-h, 11, and 12 or allyl propargyl ethers 8d-h are easily isomerized with potassium tert-butoxide (KO-t-Bu) into the corresponding allenyl derivatives 3a-h, 13, 14, and 9d-h. These compounds afford alpha-methylene-gamma-butyrolactones 7a-h, 25, and 26 by application of the sequence halogenation/dehydrohalogenation/homolytic carbocyclization. Starting from methyl vinyl ketone 1i, similar transformations lead to botryodiplodin (27) or ethoxybotryodiplodin (28).
• Rehnberg, Nicola; Magnusson, Goeran, Acta Chemica Scandinavica, 1990, vol. 44, # 4, p. 377 - 383
  作者：Rehnberg, Nicola、Magnusson, Goeran

  DOI：——

  日期：——
• REHNBERG, NICOLA;MAGNUSSON, GORAN, ACTA CHEM. SCAND., 44,(1990) N, C. 377-383
  作者：REHNBERG, NICOLA、MAGNUSSON, GORAN

  DOI：——

  日期：——