(+)-macrosphelide G | 200335-78-0

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酯类和类似物
• 英文名称: (+)-macrosphelide G
• 英文别名: macrosphelide G；(4R,7E,9R,10S,13E,16S)-9-Hydroxy-4,10,16-trimethyl-1,5,11-trioxacyclohexadeca-7,13-diene-2,6,12-trione
• CAS: 200335-78-0
• 化学式: C₁₆H₂₂O₇
• 分子量: 326.346
• InChiKey: QTVMZKJQTJNPJL-VCPJVSAUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  23
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  99.1
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  甲醇 、 4-溴苯甲酰氯 、 (+)-macrosphelide G 在 硫酸 、 吡啶 作用下， 以2.8 mg的产率得到methyl (4R,5S)-4,5-bis-(p-bromobenzoyloxy)hex-2-enoate
  参考文献：
  名称：

  Absolute stereostructures of cell-adhesion inhibitors, macrosphelides C, E–G and I, produced by a Periconia species separated from an Aplysia sea hare

  摘要：

  宏球苷E–I与已知的宏球苷A和C一起从最初从海兔Aplysia kurodai分离出的Periconia byssoides菌株中提取出来，并且宏球苷E–G和I的绝对立体结构已通过使用1D和2D NMR技术的光谱分析及一些化学转化进行阐明。此外，之前未确定的宏球苷C的绝对构型已通过X射线分析和改良的Mosher方法确立。宏球苷E–H抑制了人类白血病HL-60细胞与HUVEC的粘附。

  DOI：

  10.1039/b104337b
• 作为产物：
  描述：

  methyl (4R,5S)-4,5-dihydroxyhex-2E-enoate 在 吡啶 、 咪唑 、 4-二甲氨基吡啶 、 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 sodium hydroxide 、 sodium tetrahydroborate 、 三氯化铝 、 三丁基膦 、 2,4,6-三氯苯甲酰氯 、 D(+)-10-樟脑磺酸 、 水 、 sodium acetate 、 溶剂黄146 、 三乙胺 、 N,N'-二环己基碳二亚胺 、 锌 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 xylene 、 苯 为溶剂， 反应 62.5h， 生成 (+)-macrosphelide G
  参考文献：
  名称：

  New total syntheses of (+)-macrosphelides C, F and G

  摘要：

  The total synthesis of (+)-macrosphelide C 1 (25% overall yield in nine steps), (+)-macrosphelide F 2 (20% overall yield in nine steps) and (+)-macrosphelide G 3 (22% overall yield in nine steps) has been achieved from the chemoenzymatic reaction product (4R,5S)-4-benyloxy-5-hydroxy-(2E)-hexenoate 7. (C) 2002 Published by Flsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(02)00180-5

文献信息

• General Stereodivergent Enantioselective Total Synthetic Approach toward Macrosphelides A–G and M
  作者：Christine Häcker、Bernd Plietker

  DOI：10.1021/acs.joc.5b01171

  日期：2015.8.21

  enantioselective total synthesis algorithm for the preparation of 8 out of 13 macrosphelides within 9–11 steps starting from tert-butyl sorbate is presented. The use of a cyclic sulfate as both protecting and reactivity directing group is the key element within this algorithm. A high-pressure transesterification allows for the selective ring-enlargement of the 15-membered macrosphelides into the 16-membered

  提出了一种简单的对映选择性全合成算法，该方法可从山梨酸叔丁酯开始的9-11个步骤中，制备13种大s中的8种。使用环状硫酸盐作为保护基和反应性导向基团是该算法中的关键要素。高压酯交换反应允许将15元大环内酯选择性环扩大为16元对应物。天然产物的绝对构型通过化学合成和X射线结构分析明确分配。
• Method for synthesizing macrosphelides
  申请人：Nemoto Hideo

  公开号：US20060030720A1

  公开（公告）日：2006-02-09

  The present invention is a method for synthesizing macrosphelides represented by the following formula, and relates to the following method. The hydroxyl group of methyl 3-hydroxybutyrate is protected and reduced to alcohol. The alcohol is then oxidized to give 3-(tert-butyldimethylsilyloxy) butylaldehyde, and this aldehyde is then reacted with tert-butyl diethylphosphonoacetate to give an olefin, and then deprotected. Next, dehydrative condensation with diethylphosponoacetic acid are performed to give tert-butyl 5-[2-(diethylphosphonoyl) acetoxy] hex-2-enoate, and this compound is reacted with 3-(tert-butyldimethylsilyloxy) butylaldehyde to form a diester. Following this, deprotection is performed to give an alcohol, and dehydrative condensation of the alcohol with 3-(tert-butyldimethylsilyloxy) butyric acid gives a triester. A hydroxycarboxylic acid is yielded by deprotection, and then the hydroxycarboxylic acid is converted into a macrolactone.

  本发明是一种合成以下式子所表示的macrosphelides的方法，涉及以下方法。将甲基3-羟基丁酸酯的羟基保护并还原为醇。然后将醇氧化为3-(叔丁基二甲基硅氧基)丁基醛，然后将该醛与叔丁基二乙基膦酸酯反应形成烯烃，然后去保护基。接下来，与二乙基膦酸酸进行缩合反应，形成叔丁基5-[2-(二乙基膦酰基)乙氧基]己-2-烯酸叔丁酯，然后将该化合物与3-(叔丁基二甲基硅氧基)丁基醛反应形成二酯。随后进行去保护基反应得到醇，然后将醇与3-(叔丁基二甲基硅氧基)丁酸脱水缩合反应得到三酯。去保护基后得到羟基羧酸，然后将羟基羧酸转化为大环内酯。
• RCM mediated synthesis of macrosphelides I and G
  作者：Gangavaram V.M. Sharma、Kagita Veera Babu

  DOI：10.1016/j.tetasy.2007.08.017

  日期：2007.9

  The total synthesis of 16-membered macrolides, macraosphelides I and G, has been achieved starting from ethyl-(S)-lactate and (S)- malic acid. A combination of Jacobsen's hydrolytic kinetic resolution and Sharpless epoxidation is used for the creation of two stereogenic centres, while Yamaguchi esterification and ring-closing metathesis strategies were used for the construction of the lactone ring. (c) 2007 Elsevier Ltd. All rights reserved.
• Synthesis of macrosphelides H and G
  作者：Yuichi Kobayashi、Yong-Gang Wang

  DOI：10.1016/s0040-4039(02)00781-5

  日期：2002.6

  A compound with furyl and vinyl groups was designed as an intermediate for synthesis of macrosphelide H. The furyl group was oxidatively transformed into the key C(5)-O(10) part by a two-step conversion of (1) NBS, H2O: (2) NaClO2 without affecting the free hydroxyl group at C(3). thus furnishing the seco acid, while the Wacker oxidation at the final step was used to convert the vinyl group into acetyl group to afford macrosphelide H. This strategy was applied successfully to synthesis or macrosphelide G as well. (C) 2002 Elsevier Science Ltd. All rights reserved.
• US7265229B2
  申请人：——

  公开号：US7265229B2

  公开（公告）日：2007-09-04