7-Trifluoromethanesulfonyloxy-hept-5-ynoic acid methyl ester | 149862-39-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: 7-Trifluoromethanesulfonyloxy-hept-5-ynoic acid methyl ester
• 英文别名: 5-Heptynoic acid, 7-[[(trifluoromethyl)sulfonyl]oxy]-, methyl ester；methyl 7-(trifluoromethylsulfonyloxy)hept-5-ynoate
• CAS: 149862-39-5
• 化学式: C₉H₁₁F₃O₅S
• 分子量: 288.245
• InChiKey: PMHRWSINQJSUSM-UHFFFAOYSA-N

物化性质

• 沸点：
  305.6±42.0 °C(Predicted)
• 密度：
  1.387±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  18
• 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：
  78
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  7-Trifluoromethanesulfonyloxy-hept-5-ynoic acid methyl ester 在 5percent Pd/BaSO₄ 喹啉 、 甲基锂 、 氢气 作用下， 以 四氢呋喃 、 环己烷 、 苯 为溶剂， -30.0~40.0 ℃ 、101.33 kPa 条件下， 反应 4.83h， 生成 (Z)-7-{(1R,2R,3R)-3-(tert-Butyl-dimethyl-silanyloxy)-2-[(E)-(S)-3-(tert-butyl-dimethyl-silanyloxy)-oct-1-enyl]-6-oxo-cyclohexyl}-hept-5-enoic acid methyl ester
  参考文献：
  名称：

  Solution- and Soluble-Polymer Supported Asymmetric Syntheses of Six-Membered Ring Prostanoids

  摘要：

  An asymmetric synthesis of prostanoids containing a six-membered ring core structure (11a-homoprostaglandins), both in solution and using non-cross-linked polystyrene (NCPS) as a soluble support, was developed. Target molecule 1 was generated in a convergent fashion using a three-component coupling strategy, wherein chiral enone (R)-2 was the precursor of the central ring and the cuprate 3 and triflate 4 were used to introduce the side chains. The chiral center of (R)-2 directed the facial selectivity of the conjugate addition reaction which then dictated the stereochemical outcome of the subsequent alpha alkylation. Attachment of a six-membered ring scaffold to NCPS facilitated purification without compromising synthetic yields, still allowed H-1-NMR analysis of the intermediates in the synthesis, and provided an avenue for the construction of six-membered ring prostanoid libraries.

  DOI：

  10.1002/1521-3765(20000602)6:11<1917::aid-chem1917>3.0.co;2-7
• 作为产物：
  描述：

  三氟甲磺酸酐 、 7-羟基-5-庚炔酸甲酯 在 2,6-二叔丁基吡啶 作用下， 以 二氯甲烷 为溶剂， 生成 7-Trifluoromethanesulfonyloxy-hept-5-ynoic acid methyl ester
  参考文献：
  名称：

  可溶性聚合物支持的前列腺素类文库的合成：抗病毒活性的鉴定。

  摘要：

  前列腺素是有效的天然产物，参与许多生物过程。从类前列腺素组分的“工具箱”中“聚合产生多样性”，再加上其他聚合物支持的转化，可以构建有价值的文库。并行池策略用于组装小型前列腺素类库。疱疹家族病毒的抑制表明了发现新药的潜力。

  DOI：

  10.1021/ol991130j

文献信息

• METHOD FOR INTRODUCING SUBSTITUENT INTO alpha,beta-UNSATURATED KETONE AND METHOD FOR SYNTHESIZING PROSTAGLANDIN USING THE SAME
  申请人：NATIONAL CENTER FOR GERIATRICS AND GERONTOLOGY

  公开号：US20210355061A1

  公开（公告）日：2021-11-18

  The present invention provides a method for introducing substituents into the α-position and the β-position of an α,β-unsaturated ketone, which not only can be used for the synthesis of a prostaglandin by a three-component coupling process, but also enables synthesis of a prostaglandin in a high yield by one-pot operation without requiring the use of a large excess amount of any of the three components required for the synthesis or using a highly toxic heavy metal as a catalyst or a solvent that is highly toxic to living bodies, and a method for synthesizing a prostaglandin using the same technical means. The method for introducing substituents into an α,β-unsaturated ketone according to the present invention is a method for introducing substituents into the carbon at the α-position and the carbon at the β-position of an α,β-unsaturated ketone, including: a first step of mixing alkyllithium and trialkylalkenyl tin in which tin atom binds to the vinyl position of the alkenyl group; a second step of mixing the mixture of the first step and dialkylzinc; a third step of mixing the mixture of the second step and an α,β-unsaturated ketone; and a fourth step of mixing the mixture of the third step and a trifluoromethanesulfonate compound.

  本发明提供了一种将取代基引入α，β-不饱和酮的α位和β位的方法，不仅可用于通过三组分偶联过程合成前列腺素，还能够通过一锅法高产率合成前列腺素，而无需使用大量超量的三种合成所需组分之一，也无需使用高毒性重金属作为催化剂或对生物体高毒的溶剂，并提供了一种利用相同技术手段合成前列腺素的方法。 根据本发明，将取代基引入α，β-不饱和酮的方法是一种将取代基引入α，β-不饱和酮的α位和β位碳的方法，包括：第一步，混合烷基锂和三烷基烯基锡，其中锡原子与烯基团的乙烯位结合；第二步，混合第一步的混合物和二烷基锌；第三步，混合第二步的混合物和α，β-不饱和酮；第四步，混合第三步的混合物和三氟甲磺酸盐化合物。
• Organozinc-aided, HMPA-free, stoichiometric three-component coupling for the general synthesis of prostaglandins and stable prostacyclin analogs with biological significance
  作者：Hiroko Koyama、Atsuto Izumiseki、Masaaki Suzuki

  DOI：10.1016/j.tetlet.2019.04.037

  日期：2019.5

  method afforded protected 5,6-didehydro-PGE2, a common intermediate for the general synthesis of natural PGs and the stable artificial prostacyclin (PGI2) analog isocarbacyclin in 88% yield. The utility of the method was further applied to the syntheses of novel intermediates, which are useful for the straightforward synthesis of 15R-TIC and 15-deoxy-TIC in 79% and 86% yield, respectively.

  通过结合二甲基锌辅助的ω-侧链乙烯基锂与（R）-4-羟基-的二甲基锌辅助共轭加成反应，开发了一种三组分偶联程序，以在无HMPA和化学计量条件下构建整个前列腺素（PG）骨架。2-环戊烯酮和用α-侧链炔丙基三氟甲磺酸酯直接捕获所得的烯醇化物。二甲基锌可有效调节共轭加成和炔基化反应。因此，该方法提供了受保护的5,6-didehydro-PGE 2，这是天然PG和稳定的人工前列环素（PGI 2的一般合成的通用中间体）类似异卡巴环素，收率88％。该方法的实用性进一步应用于新型中间体的合成，这些中间体可分别以79％和86％的收率直接合成15 R -TIC和15-脱氧-TIC。
• A Practical, General Three-Component Coupling Approach to Prostaglandin and Non-Prostaglandin-Related Skeleta
  作者：Bruce H. Lipshutz、Michael R. Wood

  DOI：10.1021/ja00105a010

  日期：1994.12

  Starting with a terminal alkyne, a one-pot, six-step sequence has been developed which results in prostaglandin and related skeleta in high. yields. The method involves a transmetalation between organozirconium and cuprate species, as well as another between a copper enolate and organozincate reagent. Only catalytic amounts of the cuprate are needed. A variety of cyclic and acyclic enones participate in these multiple couplings, demonstrating that the methodology applies to far more than just the prostaglandin nucleus.
• An expedient triply convergent synthesis of prostaglandins
  作者：Owen W. Gooding

  DOI：10.1021/jo00300a048

  日期：1990.6
• Triply convergent synthesis of 15-(phenoxymethyl) and 4,5-allenyl prostaglandins. Preparation of an individual isomer of enprostil
  作者：Owen W. Gooding、Colin C. Beard、Gary F. Cooper、David Y. Jackson

  DOI：10.1021/jo00066a020

  日期：1993.7

  A triply convergent synthesis of the PGE2 derivatives 1, 3, 4, and 5, containing either the 15-(phenoxymethyl) or the 15-amyl omega side chain and the 5,6-didehydro or the 4,5-allenyl alpha side chain, is described. This two-pot method employs organocopper reagents of the type Li2RomegaCuCNMe to selectively introduce the omega side chain to enantiopure enone 6 followed by in situ trapping of the so-formed enolates as silyl enol ethers 22a and 22b. The kev step is the alkylation of regiochemically defined lithium enolates, generated from the corresponding silyl enol ethers 22a and 22b, with the unsaturated alpha side chain triflates 8b and 9c. The method was found to be general for propargylic and allenic alpha side chains but unsuccessful for the cis allylic and saturated a side chains found in PGE2 and PGE1, respectively.