球二孢菌素 | 27098-03-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 中文名称: 球二孢菌素
• 英文名称: (-)-botryodiplodin
• 英文别名: 1-[(3S,4R)-5-hydroxy-4-methyloxolan-3-yl]ethanone
• CAS: 27098-03-9
• 化学式: C₇H₁₂O₃
• 分子量: 144.17
• InChiKey: CLYSZQBIUYRLNX-WETFRILZSA-N

物化性质

• 熔点：
  51°C
• 沸点：
  202.77°C (rough estimate)
• 密度：
  1.0789 (rough estimate)
• LogP：
  0.571 (est)

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

安全信息

• 海关编码：
  2932190090

制备方法与用途

类别：易燃液体
毒性分级：高毒
急性毒性：未报道，小鼠 LD50: 40 毫克/公斤

可燃性危险特性：该物质为易燃液体；受热分解时会释放出辛辣刺激烟雾。

储运特性：应存放在通风库房内，保持低温、干燥环境，并采取防火措施，避免与食品原料混放。

灭火剂：可使用水、泡沫、沙土、二氧化碳或干粉进行扑救。

反应信息

• 作为反应物：
  描述：

  乙酸酐 、 球二孢菌素 在 吡啶 作用下， 反应 0.17h， 以0.8 mg的产率得到
  参考文献：
  名称：

  Lasiojasmonates A–C, three jasmonic acid esters produced by Lasiodiplodia sp., a grapevine pathogen

  摘要：

  In this study, a strain (BL 101) of a species of Lasiodiplodia, not yet formally described, which was isolated from declining grapevine plants showing wedge-shaped cankers, was investigated for its ability to produce in vitro bioactive secondary metabolites. From culture filtrates of this strain three jasmonic acid esters, named lasiojasmonates A-C and 16-O-acetylbotryosphaerilactones A and C were isolated together with (1R,2R)-jasmonic acid, its methyl ester, botryosphaerilactone A, (3S,4R,5R)-4-hydroxymethyl-3,5-dimethyldihydro-2-furanone and (3R,4S)-botryodiplodin. The structures of lasiojasmonates A-C were established by spectroscopic methods as (1R*,2R*,3'S*,4'R*,5'R*)-4-hydroxymethyl-3,5-dimethyldihydro-2-furanone, (1R*,2R*,3'S*,4'R*,5'R*,10'R*,12'R*,13'R*,14'S*) and (1R*,2R*,3'S*,4'R*,5'R*,10'S*,12'R*,13'R*,14'S*)-4-(4-hydroxymethyl-3,5-dimethyltetrahydro-furan-2-yloxymethyl)-3,5-dimethyldihydro-2-furanones jasmonates (1, 4 and 5). The structures of 16-O-acetylbotryosphaerilactones A and C were determined by comparison of their spectral data with those of the corresponding acetyl derivatives obtained by acetylation of botryosphaerilactone A. The metabolites isolated, except 4 and 5, were tested at 1mg/mL on leaves of grapevine cv. Cannonau and cork oak using the leaf puncture assay. They were also tested on detached grapevine leaves at 0.5mg/mL and tomato cuttings at 0.1mg/mL. In all phytotoxic assays only jasmonic acid was found to be active. All metabolites were inactive in the zootoxic assay at 50 μg/mL.

  DOI：

  10.1016/j.phytochem.2014.03.016
• 作为产物：
  描述：

  3-Bromo-4-(1,2-propadienyloxy)butan-2-one ethylene ketal 在 palladium on activated charcoal 、 18-冠醚-6 sodium hydroxide 、 sodium tetrahydroborate 、 N-溴代丁二酰亚胺(NBS) 、 (4-methylpent-4-enyl)bis(dimethylglyoximato)(pyridine)cobalt(III) 、 硫酸 、 potassium tert-butylate 、 氢气 、 silica gel 作用下， 以 乙醇 、 二氯甲烷 、 丙酮 、 苯 为溶剂， 反应 22.75h， 生成 球二孢菌素
  参考文献：
  名称：

  Allenyl ethers as precursors of .alpha.-methylene-.gamma.-butyrolactones and botryodiplodin derivatives

  摘要：

  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).

  DOI：

  10.1021/jo00073a033

文献信息

• Synthesis of (±)- and (−)-botryodiplodin using stereoselective radical cyclizations of acyclic esters and acetals
  作者：Robert Nouguier、Stéphane Gastaldi、Didier Stien、Michèle Bertrand、Félix Villar、Olivier Andrey、Philippe Renaud

  DOI：10.1016/j.tetasy.2003.06.004

  日期：2003.10

  Three different routes for the stereoselective synthesis of botryodiplodin have been investigated. The intramolecular allylation of acetals proved to be unsatisfactory due to unstable intermediates and poor stereocontrol. Zard intramolecular radical allylation of a 2-iodopropionate derivative allows the development of an expeditious synthesis of racemic botryodiplodin. The relative configuration within

  已经研究了用于葡萄孢菌素的立体选择性合成的三种不同途径。缩醛的分子内烯丙基化由于不稳定的中间体和差的立体控制而被证明是不令人满意的。2-碘代丙酸酯衍生物的Zard分子内自由基烯丙基化可以快速发展外消旋的葡萄孢单倍体。最终产品中的相对构型已通过去质子-再质子化步骤进行了校正。接下来研究了烯丙基溴缩醛的环化反应，证明其对于合成外消旋和对映体纯的葡萄球菌双孢菌素是令人满意的。通过环化宝石-二溴化物，然后立体选择性地还原由此形成的环状一溴化物，实现了良好的立体控制。
• 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）。
• 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：——