2-hydroxy-3-methoxy-5-methylhex-5-enoic acid methyl ester | 866454-62-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 2-hydroxy-3-methoxy-5-methylhex-5-enoic acid methyl ester
• 英文别名: (2S,3S)-methyl 2-hydroxy-3-methoxy-5-methylhex-5-enoate；methyl(2S,3S)-2-hydroxy-3-methoxy-5-methylhex-5-enoate；(S,S)-methyl psymberate；methyl (2S,3S)-2-hydroxy-3-methoxy-5-methylhex-5-enoate
• CAS: 866454-62-8
• 化学式: C₉H₁₆O₄
• 分子量: 188.224
• InChiKey: OHHIDMQUORCCBD-YUMQZZPRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-hydroxy-3-methoxy-5-methylhex-5-enoic acid methyl ester 在 硫酸 作用下， 以 甲醇 为溶剂， 反应 12.0h， 以100%的产率得到(2S,3S)-3-methoxy-5,5-dimethyltetrahydrofuran-2-carboxylic acid methyl ester
  参考文献：
  名称：

  Stereochemical Assignment of the C₁−C₆ Fragment of Psymberin by Synthesis and Natural Product Degradation

  摘要：

  Psymberin is a sponge-derived natural product that shows striking selectivity as a cytotoxic agent. Conformational mobility has precluded stereochemical assignment for the acyl fragment of this molecule (psymberic acid) by NMR. Herein we report stereoselective syntheses of all four stereoisomers of psymberic acid. A comparison of the acid-mediated cyclization products of these compounds to the product of psymberin's acidic methanolysis showed the stereochemical configuration of this fragment to be 4S, 5S.

  DOI：

  10.1021/ol051396s
• 作为产物：
  描述：

  methyl (2S,3S)-2-(benzyloxy)-3-hydroxy-6-((4-methoxybenzyl)oxy)-5-methylhexanoate 在 2,6-二叔丁基吡啶 、 2-硝基苯基丝氰酸酯 、 三丁基膦 、 palladium 10% on activated carbon 、 氢气 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙酸乙酯 为溶剂， 25.0 ℃ 、275.8 kPa 条件下， 反应 48.0h， 生成 2-hydroxy-3-methoxy-5-methylhex-5-enoic acid methyl ester
  参考文献：
  名称：

  使用 Evans 手性助剂不对称合成 psymberin 的 C1-C6 部分

  摘要：

  强效细胞毒剂 psymberin 的 C1-C6 区域已被合成。合成的关键转化是辅助控制地将 Sn(II)-乙醇酸烯醇化物添加到醛中以产生反羟醛产物，并利用有机硒化学将伯醇转化为末端烯烃。

  DOI：

  10.1016/j.tetlet.2013.05.153

文献信息

• Synthesis of 8-Desmethoxy Psymberin: A Putative Biosynthetic Intermediate Towards the Marine Polyketide Psymberin
  作者：Max Bielitza、Jörg Pietruszka

  DOI：10.1002/chem.201203149

  日期：2013.6.17

  tetrahydropyran core was an enantioselective catalytic Mukaiyama aldol reaction using a titanium(IV)–BINOL catalyst system. syn‐Selective reduction followed by ozonolysis led to a rapid assembly of the tetrahydropyran ring. This flexible approach also allows the synthesis of similar fragments of other complex molecules such as bryostatins and pederins. The syn‐selective coupling between the tetrahydropyran

  描述了假单胞菌素的假定的生物合成前体的合成，包括天然产物的正式合成。致密地官能化的四氢吡喃核的关键步骤是使用钛（IV）-BINOL催化剂体系进行对映选择性催化Mukaiyama aldol反应。syn-选择性还原，然后进行臭氧分解，导致四氢吡喃环快速组装。这种灵活的方法还可以合成其他复杂分子的类似片段，例如bryostatin和pederins。该SYN四氢吡喃与芳族醛之间的选择性偶联是通过硼介导的羟醛反应实现的，随后进行进一步的转化以完成前体的合成以及天然产物的正式合成。
• Chemoenzymatic Synthesis of (Protected) Psymberic Acid
  作者：Jörg Pietruszka、Robert Christian Simon

  DOI：10.1002/ejoc.200900292

  日期：2009.7

  Two alternative approaches to the side-chain of psymberin (1), psymberic acid (5), have been developed starting from either racemic or enantiopure acetal 6. A five-step chemoenzymatic route provided the PMB-protected acid (S,S)-16 required for the coupling that should ultimately lead to the natural product 1. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

  已经从外消旋或对映纯缩醛 6 开始开发了 psymberin (1) 侧链的两种替代方法 psymberic acid (5)。五步化学酶促路线提供了 PMB 保护的酸 (S,S)-最终产生天然产物 1 的偶联所需的 16。（© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009）
• Henssen, Birgit; Kasparyan, Elena; Marten, Gernot, Heterocycles, 2007, vol. 74, # C, p. 245 - 249
  作者：Henssen, Birgit、Kasparyan, Elena、Marten, Gernot、Pietruszka, Joerg

  DOI：——

  日期：——
• Asymmetric synthesis of the C1–C6 portion of the psymberin using an Evans chiral auxiliary
  作者：Ashutosh Pal、Zhenghong Peng、Paul T. Schuber、Basvoju A. Bhanu Prasad、William G. Bornmann

  DOI：10.1016/j.tetlet.2013.05.153

  日期：2013.10

  cytotoxic agent psymberin has been synthesized. The key transformations of the synthesis are an auxiliary-controlled addition of a Sn(II)-glycolate enolate to an aldehyde to yield the anti-aldol product and transforming the primary alcohol into a terminal olefin utilizing organoselenium chemistry.

  强效细胞毒剂 psymberin 的 C1-C6 区域已被合成。合成的关键转化是辅助控制地将 Sn(II)-乙醇酸烯醇化物添加到醛中以产生反羟醛产物，并利用有机硒化学将伯醇转化为末端烯烃。
• Stereochemical Assignment of the C₁−C₆ Fragment of Psymberin by Synthesis and Natural Product Degradation
  作者：Michael E. Green、Jason C. Rech、Paul E. Floreancig

  DOI：10.1021/ol051396s

  日期：2005.9.1

  Psymberin is a sponge-derived natural product that shows striking selectivity as a cytotoxic agent. Conformational mobility has precluded stereochemical assignment for the acyl fragment of this molecule (psymberic acid) by NMR. Herein we report stereoselective syntheses of all four stereoisomers of psymberic acid. A comparison of the acid-mediated cyclization products of these compounds to the product of psymberin's acidic methanolysis showed the stereochemical configuration of this fragment to be 4S, 5S.