(2S,3S,4E)-2-carboxy-4-[(2E,5R)-5-carboxy-1-methyl-2-hexen-1-ylidene]-3-pyrrolidineacetic acid | 188346-81-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (2S,3S,4E)-2-carboxy-4-[(2E,5R)-5-carboxy-1-methyl-2-hexen-1-ylidene]-3-pyrrolidineacetic acid
• 英文别名: (2S,3S,5'R)-3-carboxymethyl-4-(5-carboxy-1-methyl-hex-2-enylidene)pyrrolidine-2-carboxylic acid；isodomoic acid G；5'R-isodomoic acid G；(2S,3S,4E)-4-[(E,6R)-6-carboxyhept-3-en-2-ylidene]-3-(carboxymethyl)pyrrolidine-2-carboxylic acid
• CAS: 188346-81-8
• 化学式: C₁₅H₂₁NO₆
• 分子量: 311.335
• InChiKey: MKCCCBSBSRCARB-NMWGDLGCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.8
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  124
• 氢给体数：
  4
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  (S)-4-benzyl-3-((R)-2-methylpent-4-ynoyl)oxazolidin-2-one 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 sodium dihydrogenphosphate 、 20% sodium on mercury 、 四丁基氟化铵 、 水 、 sodium methylate 、 lithium hydroxide 作用下， 以 四氢呋喃 、 甲醇 、 5,5-dimethyl-1,3-cyclohexadiene 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 21.5h， 生成 (2S,3S,4E)-2-carboxy-4-[(2E,5R)-5-carboxy-1-methyl-2-hexen-1-ylidene]-3-pyrrolidineacetic acid
  参考文献：
  名称：

  Stereocontrolled Total Syntheses of Isodomoic Acids G and H via a Unified Strategy

  摘要：

  Marine neuroexcitatory compounds isodomoic acids G and H were efficiently synthesized from a common intermediate using a silicon-based cross-coupling reaction. Dividing each target compound into the core fragment and the side-chain fragment enabled the synthesis to be convergent. The trans-2,3-disubstituted pyrrolidine core fragment was accessed through a diastereoselective rhodium-catalyzed carbonylative silylcarbocyclization reaction of a vinylglycine-derived 1,6-enyne. A stereochemically divergent desilylative iodination reaction was developed to convert the cyclization product to both E- and Z-alkenyl iodides, which would eventually lead to isodomoic acid G and isodomoic acid H, respectively. The late-stage alkenyl alkenyl silicon-based cross-coupling reaction uniting the core alkenyl iodides and the side-chain alkenylsilanol was achieved under mild conditions. Finally, two mild deprotections afforded the target molecules.

  DOI：

  10.1021/jo101790z

文献信息

• Total Syntheses of Isodomoic Acids G and H: An Exercise in Tetrasubstituted Alkene Synthesis
  作者：Yike Ni、Refaie M. Kassab、Maxim V. Chevliakov、John Montgomery

  DOI：10.1021/ja907931u

  日期：2009.12.9

  authentic material. A nickel-catalyzed cyclization constructs the pyrrolidine ring while simultaneously establishing either the E or Z stereochemistry of an exocyclic tetrasubstituted alkene. Stereoselective assembly of both the E- and Z-alkenes of the natural products is made possible by a predictable strategy that alters the timing of substituent introduction to control alkene stereochemistry.

  吡咯烷三酸天然产物异牙酸 G 和 H 的统一方法已被开发。完成了两种天然产物的全合成，并通过将 5'-(R) 和 5'-(S) 异构体与真实材料样品进行比较来确定异糖酸 G 的正确立体结构。镍催化的环化构建吡咯烷环，同时建立环外四取代烯烃的 E 或 Z 立体化学。通过改变取代基引入时间以控制烯烃立体化学的可预测策略，使天然产物的 E-和 Z-烯烃的立体选择性组装成为可能。
• Total Syntheses of Isodomoic Acids G and H
  作者：Scott E. Denmark、Jack Hung-Chang Liu、Joseck M. Muhuhi

  DOI：10.1021/ja9063475

  日期：2009.10.14

  The total syntheses of marine natural products belonging to the kainoid family, isodomoic acids G and H, are described. The strategic connection involves a sequential silylcarbocyclization/silicon-based cross-coupling process. These total syntheses were achieved efficiently via a 12- and a 13-step, longest-linear sequence, respectively. The key transformations include a diastereoselective rhodium-catalyzed

  描述了属于 kainoid 家族、isodomoic 酸 G 和 H 的海洋天然产物的全合成。战略联系涉及顺序的甲硅烷基碳环化/基于硅的交叉偶联过程。这些全合成分别通过 12 步和 13 步最长线性序列有效实现。关键转化包括（l）-乙烯基甘氨酸衍生的 1,6-烯炔的非对映选择性铑催化羰基化甲硅烷基碳环化反应、脱甲硅烷基碘化反应以及基于烯基-烯基硅的交叉偶联反应。在研究碘脱甲硅烷基化反应过程中获得的机械洞察力使碘的立体控制引入与双键构型的反转或保留成为可能。