methyl 2-(1'-mesyloxycyclopropyl)acetate | 142599-61-9

• 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: methyl 2-(1'-mesyloxycyclopropyl)acetate
• 英文别名: methyl (1-methylsulfonyloxycyclopropyl)acetate；methyl 2-(1-methylsulfonyloxycyclopropyl)acetate
• CAS: 142599-61-9
• 化学式: C₇H₁₂O₅S
• 分子量: 208.235
• InChiKey: OAQGHJBGWCGWHL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  78
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 2-(1'-mesyloxycyclopropyl)acetate 在 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以60%的产率得到2-(chloromethyl)acrylic acid methyl ester
  参考文献：
  名称：

  Synthesis of methyl 3-bromomethylbut-3-enoate and its reactions with aldehydes and tributylchlorostannane in the presence of zinc

  摘要：

  Methyl 3-bromomethylbut-3-enoate smoothly reacted with prenal, beta-ionylideneacetaldehyde, benzyloxyacetaldehyde, and tributylchlorostannane in the presence of zinc and aqueous ammonium chloride in tetrahydrofuran to give the corresponding delta-hydroxy-beta-methylidenecarboxylic acid esters. In the absence of ammonium chloride, satisfactory yields of the products were obtained only in the reactions with prenal and benzyloxyacetaldehyde; these reactions involved lactonization of intermediate delta-hydroxy-beta-methylidenecarboxylic acid esters, and the double carbon-carbon bond migrated to the conjugated position with the lactone carbonyl group. The condensation of beta-ionylideneacetaldehyde with methyl 3-bromomethylbut-3-enoate was successfully used to obtain isotretinoin. Initial methyl 3-bromomethylbut-3-enoate was synthesized in a good yield from readily accessible ethyl 3,3-diethoxypropionate via cyclopropanation with ethylmagnesium bromide in the presence of titanium tetra(isopropoxide), oxidation of the acetal moiety to ester, and cleavage of the cyclopropane ring in intermediate methyl (1-methylsulfonyloxycyclopropyl)acetate.

  DOI：

  10.1134/s1070428008090029
• 作为产物：
  描述：

  [1-(2-oxoethyl)cyclopropyl] methanesulfonate 在 硫酸 、 双氧水 作用下， 以 四氢呋喃 为溶剂， 反应 26.0h， 生成 methyl 2-(1'-mesyloxycyclopropyl)acetate
  参考文献：
  名称：

  用于有机合成的环丙基积木，第 100 部分。环丙叉乙酸酯的高级合成——用于有机合成的多功能多功能积木

  摘要：

  已开发出一种可重复性良好且价格低廉的环亚丙基乙酸酯 2-4 制备方法。关键中间体 2-(1'-甲磺氧基环丙基)乙酸 (8)，由苯乙酸甲酯 (1) 或 3,3-二甲氧基丙酸 (5-Me) 和 3,3-二乙氧基丙酸 (5-Et) 按顺序生产Kulinkovich 的还原环丙烷化、甲磺酰化和氧化裂解或裂解和氧化分别转化为苄酯 11b，或通过原位形成的酰氯氯化（溴化）。α-氯- 12a 和 α-溴酯 12b 通过用三乙胺处理脱氢甲磺酸化，得到 2-氯-2-亚环丙基乙酸甲酯 (3-Me) 和 2-溴类似物 4-Me，总产率为 68% (从 1 (5-Me, 5-Et) 开始，分别为 65%、68%) 和 52% (49%、51%)。

  DOI：

  10.1002/adsc.200404025

文献信息

• Methyl 3-bromomethyl-3-butenoate as an isopentane building block for the stereoselective preparation of (S)-4-methyl-3,6-dihydro-2H-pyran-2-carbaldehyde and (+)-faranal
  作者：Iryna V. Mineyeva、Oleg G. Kulinkovich

  DOI：10.1016/j.tetlet.2010.01.120

  日期：2010.4

  (S)-4-Methyl-3,6-dihydro-2H-pyran-2-carbaldehyde (3), the common intermediate in the syntheses of the C17-C27 subunit of laulimalide (4) and (+)-faranal (5), the trail pheromone of the pharaoh ant, Monomorium pharaonis, were obtained via transformation of methyl 3-bromomethyl-3-butenoate (1) into allylstannane 2 and subsequent allylation of (benzyloxy)acetaldehyde (6) in accordance with the Keck procedure as the key steps. (C) 2010 Elsevier Ltd. All rights reserved.
• Cyclopropane intermediates in the synthesis of chiral alcohols with methyl-branched carbon skeleton. Application in the synthesis of insect pheromones
  作者：V. N. Kovalenko、I. V. Mineeva

  DOI：10.1134/s1070428014070033

  日期：2014.7
• Synthesis of (2S)-4-Methyl- and (2S)-4-Methyl-6-oxo-3,6-dihydro-2H-pyran-2-carbaldehydes as Precursors to C22–C27 Fragments of Fijianolides and Their Synthetic Analogs
  作者：I. V. Mineeva

  DOI：10.1134/s1070428018090130

  日期：2018.9

  New schemes of synthesis of (2S)-4-methyl- and (2S)-4-methyl-6-oxo-3,6-dihydro-2H-pyran-2-carbaldehydes have been developed with the goal of obtaining C-22-C-27 fragments of fijianolides and their synthetic analogs on the basis of transformations of cyclopropanol intermediates. The C-22-C-27 block of fijianolides A and B has been synthesized.
• New approach to the synthesis of macrocyclic core of cytotoxic lactone (+)-neopeltolide. Synthesis of C7–C14 segment basing on cyclopropanol intermediates
  作者：I. V. Mineeva

  DOI：10.1134/s1070428015080023

  日期：2015.8

  A new retrosynthetic procedure was developed for the synthesis of the macrocyclic core of a cytotoxic lactone (+)-neopeltolide utilizing cyclopropanol intermediates. The synthesis was suggested and carried out of the C-7-C-16 segment of (+)-neopeltolide to obtain (4S,6S)-6-[(2S)-2-hydroxypentyl]-4-methyltetrahydro-2H-pyran-2-one. The possibility was demonstrated of a formal synthesis based on the obtained product of the potential antitumor pharmaceutical (+)-neopeltolide.