syringolide 1 | 147716-82-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 呋喃类
• 英文名称: syringolide 1
• 英文别名: (1R,4R,5S,7R,8S)-4,7-dihydroxy-7-pentyl-2,6,10-trioxatricyclo[6.3.0.01,5]undecan-9-one
• CAS: 147716-82-3
• 化学式: C₁₃H₂₀O₆
• 分子量: 272.298
• InChiKey: KFHLOSLXXIXBMW-YTCQTTRASA-N

物化性质

• 沸点：
  527.4±50.0 °C(Predicted)
• 密度：
  1.35±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  85.2
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  syringolide 1 在 palladium on activated charcoal 4-二甲氨基吡啶 、 Dowex 50W-X₈*HCl 、 氢气 、 二甲基氨基丙基乙基碳酰胺 作用下， 以 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 19.0h， 生成 [(1R,4R,5S,7R,8S)-7-hydroxy-9-oxo-7-pentyl-2,6,10-trioxatricyclo[6.3.0.01,5]undecan-4-yl] 2-(3,4,5-trimethoxyphenyl)acetate
  参考文献：
  名称：

  Synthesis of syringolide 1 ketals and esters for receptor studies

  摘要：

  The syringolides, specified by avirulence gene D from Pseudomonas syringae, elicit a disease defense reaction only in soybean cultivars carrying the Rpg4 disease resistance gene. In order to identify structural features important for elicitor activity and construct highly labelled elicitor-active probes, several syringolide esters and ketals were synthesized. Alteration of the C-3 hemiketal group of syringolide 1 abolished elicitor activity, but ester derivatives based on the C-4' hydroxy group all retained activity. [I-125]4'-(2-iodo-3,4,5-trimethoxyphenylacetyl) syringolide 1 was prepared for receptor studies. Copyright (C) 1996 Elsevier Science Ltd

  DOI：

  10.1016/s0031-9422(96)00530-4
• 作为产物：
  描述：

  D-吡喃木糖 在 吡啶 、 4-二甲氨基吡啶 、 水 、 四氯化钛 、 copper(II) sulfate 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 176.0h， 生成 syringolide 1
  参考文献：
  名称：

  Concise Syntheses of (−)- and (+)-Syringolide 1 and (−)-Δ⁷-Syringolide 1

  摘要：

  (-)-和(+)-松柏醇内酯1已从2,3-O-异丙叉基-β-赤-五碳糖醛酸(1)中合成，而1则分别由D-或L-木糖简便制得。1与3-氧基辛酸进行缩合，随后将酯与TFA:H2O（9:1）处理，得到松柏醇内酯1，两步收率为6.3%。按照相同的合成路线，用3-氧基-7-辛烯酸替代3-氧基辛酸，得到了(-)-Δ(7)-松柏醇内酯1，收率为5.8%。还制备了阿拉伯糖和果糖的初级P-酮酸酯，以测试生物模拟环化反应生成松柏醇内酯类似物的选择性。

  DOI：

  10.1021/jo970461b

文献信息

• Synthesis of (−)-syringolides 1 and 2
  作者：Shigefumi Kuwahara、Masahiko Moriguchi、Kazuhiro Miyagawa、Masako Konno、Osamu Kodama

  DOI：10.1016/0040-4020(95)00488-t

  日期：1995.8

  enantioselective synthesis of (−)-syringolides 1 and 2 which were isolated as specific elicitors produced by Pseudomonas syringae pv. tomato was accomplished in 11 steps from diethyl d tartrate. The specific rotations of synthetic samples were in good accord with those of the natural syringolides, and synthetic syringolide 2 showed almost the same biological activity as that of natural syringolide 2.

  （-）-丁香油酸酯1和2的对映选择性合成，其作为丁香假单胞菌pv产生的特定引发剂被分离。从酒石酸二乙酯分11步完成番茄。合成样品的比旋光度与天然丁香酚的旋光度非常一致，合成丁香酚2的生物活性几乎与天然丁香酚2的生物活性相同。
• Asymmetric total synthesis of syringolide 1, a nonproteinaceous elicitor
  作者：Jun Ishihara、Tetsuya Sugimoto、Akio Murai

  DOI：10.1016/s0040-4020(97)10062-x

  日期：1997.11

  An asymmetric synthesis of syringolide 1, one of the elicitors produced by Pseudomonas syringae pv. tomato, is described. It was synthesized from 2-(1-oxoethyl)-2-buten-4-olide via 1,4-addition of alkenyl cuprate, asymmetric dihydroxylation, and intramolecular Michael reaction.

  丁香酚1的不对称合成，是丁香假单胞菌PV产生的一种引发剂。番茄，被描述。它是由2-（1-氧乙基）-2-丁烯-4-油化物经1,4-加成的烯基铜酸盐，不对称的二羟基化和分子内的迈克尔反应合成的。
• Efficient synthesis of syringolides, secosyrins, and syributins through a common approach
  作者：Anastasia-Aikaterini C. Varvogli、Ioannis N. Karagiannis、Alexandros E. Koumbis

  DOI：10.1016/j.tet.2008.11.079

  日期：2009.1

  A new common synthetic approach toward the elicitors syringolides and their related natural products, secosyrins and syributins, is described here. This uses d-arabinose as starting material and efficiently delivers the targeted compounds through a sequential tandem HWE olefination–lactonization process and an IHMA reaction.

  本文介绍了诱导子丁香油苷及其相关天然产物，二十二醛和丁香苷的一种新的通用合成方法。它以d-阿拉伯糖为起始原料，并通过顺序的串联HWE烯化-内酯化过程和IHMA反应有效地递送目标化合物。
• An improved synthesis of (−)-syringolides and X-ray structural characterization of synthetic (−)-syringolide 1
  作者：Pei Yu、Qi-Guang Wang、Thomas C.W. Mak、Henry N.C. Wong

  DOI：10.1016/s0040-4020(97)10401-x

  日期：1998.2

  On treatment with 10% HF, butenolides 4a and 4b afforded enantiopure (−)-syringolides 1 (1a) and 2 (1b) respectively in much higher yields. Unprecedentedly, the cyclic acetal 5a was also converted to 1a by reacting with an excess of p-TsOH. The structure of the synthetic (−)-syringolide 1 (1a) was substantiated by an X-ray crystallographic study.

  在用10％HF处理时，丁烯内酯4a和4b分别以高得多的产率提供了对映纯（-）-丁香油酯1（1a）和2（1b）。前所未有地，通过与过量的p-TsOH反应，环状缩醛5a也被转化为1a。通过X射线晶体学研究证实了合成的（-）-丁香油精1（1a）的结构。
• Enantioselective Syntheses of Syributin 1 and Novel C-Glycosidic Elicitors Syringolides 1 and 2
  作者：Toshio Honda、Hirotake Mizutani、Kazuo Kanai

  DOI：10.1021/jo961362l

  日期：1996.1.1

  Concise enantioselective syntheses of syributin 1 (3) and the novel nonproteinaceous C-glycosidic elicitors syringolides 1 and 2 (1 and 2, respectively), isolated from Pseudomonas syringae pv. tomato, are described. Syributin 1 was synthesized in one step by the Sharpless catalytic asymmetric dihydroxylation (AD reaction) of (1'E)-3-(3'-(octanoyloxy)-1'-propenyl)but-2-en-4-olide (13) in 72% yield with >98% ee. Furthermore, alkylation of (1'R,2'R)-3-[1'-(tert-butyldimethylsiloxy)-2,3'- (isopropylidenedioxy)propyl]but-2-en-4-olide (20), prepared from (1'E)-3-[3'-(tert-butyldimethylsiloxy)-1'-propenyl]but-2-en-4-olide (11) by the AD reaction, with hexanal or octanal by Jefford's procedure at the a position to the lactone carbonyl group gave adduct 21 or 22 in good yield. Oxidation of 21 or 2;2, followed by removal of the protecting groups, provided syringolide 1 or 2, respectively.