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基于末端碘氧化炔烃的 1-Iodoalkynes、12-Diiodoalkenes、11、2 Triiodoalkenes 的 Chemoselective 制备

Published: September 12, 2018
doi:
10.3791/58063
, , , ,
1School of Chemical Engineering and Light Industry,Guangdong University of Technology, 2Department of Chemistry, Graduate School of Science,Kyoto University

Summary

本文介绍了用高价碘试剂对炔烃末氧化碘的详细协议, chemoselectively 提供了 1 iodoalkynes、12 diiodoalkenes、11、2 triiodoalkenes。

Abstract

我们提出了 chemoselective 合成 1-(iodoethynyl)-4-甲苯, 1-(12-diiodovinyl)-4-甲苯, 1-甲基-4-(12, 2-triiodovinyl) 苯作为实际 chemoselective 制备 1-iodoalkynes 的典型例子, 12-diiodoalkenes 和 11, 2-triiodoalkenes 从 chemoselective 碘的终端炔烃介导的高价碘试剂。用p-tolylethyne 作为模型基质筛选各种碘源和/或高价碘试剂, 证实了 chemoselectivity。四丁基碘化 (TBAI) 和 (diacetoxyiodo) 苯 (PIDA) 的组合选择性地产生 1-iodoalkynes, 而基和 PIDA 的组合产生 12-diiodoalkenes。基于 TBAI-PIDA 和 PIDA 的单壶合成, 产生相应的11、2-triiodoalkenes。这些协议随后被应用于合成重要的芳香族和脂质体 1-iodoalkynes, 12-diiodoalkenes 和 11, 2-triiodoalkenes, 得到了良好的产量和优良的 chemoselectivity。

Introduction

Iodoalkynes 和 iodoalkenes 广泛应用于有机合成1、2、3、4、生物活性物质的重要前体和积木, 并在合成材料和复杂分子给出了转换 C I 键5,6,7,8的容易。近年来, 炔烃的氧化碘越来越多地引起了 iodoalkyne 和 iodoalkene 衍生物的合成。迄今为止, 使用金属催化剂的有效方法9、10、11、12、高价-碘催化剂13、14、阳极氧化系统15、离子液体系统16, 基 (或 I2)-氧化剂组合17,18,19,20, 超声波21, 相转移催化剂22, n-iodosuccinimide9,22,23,24,25, N-邓布利多26,27,28,29,30,31, 格利雅试剂32, 和啉催化剂17,33,24,35已开发为碘的炔烃。最近, 我们报告了一个实用的和 chemoselective 的协议, 合成 1-iodoalkynes, 12-diiodoalkenes, 11, 2-triiodoalkenes36。该方法具有绿色实用的特点: (1) 高价碘催化剂作为氧化功能化试剂的毒性较低, 与其他传统的重金属元素氧化剂37、38、 39,40,41,42, 和 (2) TBAI 和/或基被用作碘源。此外, 在温和的条件下, 我们的系统具有良好的选择性。chemoselective 合成 1-iodoalkynes, 12-diiodoalkenes 和 11, 2 triiodoalkenes 需要精确控制各种因素, 包括组成, 氧化剂, 碘源, 和溶剂。其中, 碘源是反应 chemoselectivity 的最重要因素。在对碘源和溶剂的几种类型和荷载进行筛选后, 确定并建立了三种方法。首先, TBAI 作为碘源结合 PIDA (TBAI PIDA) 是选择性的合成 1-iodoalkynes。或者, 用 PIDA 系统有效地获得 12-diiodoalkenes。两种方法均能提供高产、高 chemoselectivity 的相应产品。相应的三 iodinationproducts, i., 11, 2-triiodoalkenes, 得到了良好的产量从一锅合成, 结合了 TBAI-PIDA 和奇 PIDA 系统36。

在这里, 我们将演示如何从 1-iodoalkynes 到 12-diiodoalkenes 和 11, 2-triiodoalkenes 在类似的反应条件下, chemoselectivity 碘的炔烃, 突出精确的控制, 可以通过明智地选择氧化剂, 碘源, 和溶剂施加。针对这种新型合成技术的发展, 对tolylethyne 作了模型基质。虽然以下协议的重点是合成 1-(iodoethynyl)-4-甲苯, (E)-1-(12-diiodovinyl)-4-甲苯和 1-甲基-4-(12, 2-triiodovinyl) 苯, 这些化合物代表 1-iodoalkynes, 12-diiodoalkenes 和 11, 2-triiodoalkenes,即, 协议是广泛的范围内, 同样的技术可以适用于 chemoselective 碘的芳香和脂肪族终端炔烃36。

使用的试剂在 chemoselective 碘的终端炔烃和小偏差的技术所描述的结果, 对目标产品的显著差异。例如, 从 TBAI 到基的碘源的变化和溶剂的变化从 ch3cn 到 ch3cn-H2O 对碘的 chemoselectivity 产生了戏剧性的影响。详细的议定书旨在帮助外地的新从业者与终端炔烃的 chemoselective 碘, 以避免在合成 1-iodoalkynes、12-diiodoalkenes 和11、2-triiodoalkenes 过程中出现许多常见的缺陷。

Protocol

1. 合成 1-(Iodoethynyl)-4-甲苯 (2, 1-Iodoalkynes) 添加133毫克 (0.36 毫摩尔) 的 TBAI 和3毫升的 CH3CN 到一个反应管, 其中含有磁性搅拌杆, 这是开放的空气。然后, 用微量泵在混合物中加入 38 μ( 0.3 毫摩尔) 的 tolylethyne。 添加96.6 毫克 (0.3 毫摩尔) 的 PIDA, 以强力搅拌反应混合物10个部分在20分钟的时间内使用刮刀。 在室温下搅拌反应混合物3小时。 将产生的混?…

Representative Results

chemoselective 合成 1-iodoalkynes, 12-diiodoalkenes 和 11, 2-triiodoalkenes 的基础上的氧化碘的ptolylethyne 总结在图 1。所有的反应都暴露在空气中。本研究中的所有化合物均采用1H 和13C 核磁共振波谱、质谱和 HPLC 法, 以获得产物的结构和反应的选择性, 并探讨其纯度。所获得的产品稳定后, 在4°c 在一个冰箱四月, i. e., 高效液相色谱和1H ?…

Discussion

1-Iodoalkynes, 12-diiodoalkenes 和 11, 2-triiodoalkenes 可 chemoselectively 合成使用高价碘试剂作为有效的调解人氧化碘 (s)。这些 chemoselective 碘协议最关键的因素是碘源的性质和负载, 以及溶剂。例如, 1-iodoalkyne 2被获得作为主要产品 (52% 产量), 当 TBAI (2.5 equiv 装载) 被选择作为碘来源与甲醇结合作为溶剂 (2:3:4= 90:5: 5)。在将碘源转化为基时, 没有观察到这种选择?…

Divulgaciones

The authors have nothing to disclose.

Acknowledgements

这项工作得到了中国国家自然科学基金 (21502023) 的支持。

Materials

4-ethynyltoluene,98% Energy Chemical D080006
phenylacetylene,98% Energy Chemical W330041
1-ethynyl-4-methoxybenzene,98% Energy Chemical D080007
1-ethynyl-4-fluorobenzene,98% Energy Chemical D080005
4-(Trifluoromethyl)phenylacetylene,98% Energy Chemical W320273
4-Ethynylbenzoic acid methyl ester,97% Energy Chemical A020720
3-Aminophenylacetylene,97% Energy Chemical D080001
3-Butyn-1-ol,98% Energy Chemical A040031
Propargylacetate,98% Energy Chemical L10031
Tetrabutylammonium Iodide,98% Energy Chemical E010070
Potassium iodide,98% Energy Chemical E010364
(diacetoxyiodo)benzene,99% Energy Chemical A020180
acetonitrile, HPLC grade fischer A998-4
magnetic stirrer IKA
rotary evaporator Buchi
Bruker AVANCE III 400 MHz Superconducting Fourier Bruker
High-performance liquid chromatography Shimadzu
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Tags

Chemoselective IodinationTerminal Alkynes1-iodoalkynes12-diiodoalkenes112-triiodoalkenesHypervalent Iodine CatalystsTBAIKIP-tolylethynePIDAAqueous WorkupSilica Gel Chromatography

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Li, Y., Huang, D., Huang, J., Liu, Y., Maruoka, K. Chemoselective Preparation of 1-Iodoalkynes, 1,2-Diiodoalkenes, and 1,1,2-Triiodoalkenes Based on the Oxidative Iodination of Terminal Alkynes. J. Vis. Exp. (139), e58063, doi:10.3791/58063 (2018).
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