争取能在百度搜索到把青春献给代码的你;一个年轻程序员的渺小梦想-杨永飞
NOTES DETAIL
康 · 学术 | Reaction of the Day No. 171
 dzwdffxh        537

Palladium Copper Dual Catalysis for Cross-coupling of Aryl(trialkyl)silanes with Aryl Bromides

Takeshi Komiyama, Yasunori Minami, Yuki Furuya, and Tamejiro Hiyama

Department of Applied Chemistry, Chuo University

Research and Development Initiative, Chuo University

Angew. Chem. Int. Ed. 2018, 57, 1987.

Recommended by Shi Li_MOC

KEY WORDS: Arene, Copper, Cross-coupling, Palladium, Silanes

ABSTRACT: Although aryl(trialkyl)silanes are apparently ideal organometalic reagents for the cross-coupling reaction due to robustness, low toxicity, solubility, and easy accessibility, they are generally an inert cross-coupling nucleophile. Disclosed herein is that a palladium/copper catalytic system achieves the desired cross coupling of aryl-SiMe3, -SiEt3, -SiMe2(t-Bu), and -Si(i-Pr)3 with aryl bromides, allowing application to the sequential C–H and C–Si bond arylation of thiophenes and the synthesis of poly(thiophenefluorene)s.

Pd/Cu-catalyzed Reaction of 1a with 2a

Scope of Substrates

Application in Sequential Arylation via C–H/C–Si Activation:

Summary and Comments:

交叉偶联反应中以芳基硅代替芳基锡或硼酸等具有稳定性好、溶解度高、低毒、操作方便等优点,但芳基硅往往表现出比较低的反应活性。2016年日本中央大学Y. Minami和T. Hiyama等发展了Cu(II)催化的芳基硅与芳基碘代物的交叉偶联反应,但该反应条件苛刻,需要芳基碘作为底物也限制了其应用。最近该小组又报道了Pd/Cu协同催化的芳基硅与芳基溴代物的交叉偶联反应。该反应对于多种芳基三烷基硅如ArTMS, ArTES, ArTBS, ArTIPS等以及各种芳基或杂芳基溴如苯、萘、噻吩、吡啶等均适用,甚至芳基氯也可以反应。作者推测反应中加入的当量CsF和催化量的CuF2分别对C-Si键的断裂重组以及硅烷与Pd络合物的转金属过程起到了重要作用,虽然反应机理尚不十分清楚,但无疑该研究对有机硅参与的交叉偶联反应进行了有效的拓展。


Among various organometallic nucleophiles in cross-coupling reactions, such as aryl boronic acids or stannes etc, organo(trialkyl)silanes have ideal characteristics in stability, high solubility in various organic solvents, non-toxicity, easy handling and high accessibility. But it usually has lower reactivity. In 2016, Y. Minami and T. Hiyama developed a direct cross-coupling of aryltrialkylsilanes with iodoarenes by using a copper(II) catalyst. Recently they reported Pd/Cu dual catalysis undergoes the cross-coupling of aryl(trialkyl)silanes with bromo/chloro arenes under mild conditions. A wide variety of silyl groups such as TMS, TES, TBS and TIPS as well as various aryl groups in both coupling partners are found to be applicable to the dual catalytic system. Although further elucidation of the reaction mechanism is necessary, this study has no doubt effectively expanded the cross-coupling reaction involving organosilicon.


所属标签: 笔记

2 条评论

  • 梅子 2018-05-23 05:41:43

    恶棍天使,约不

  • 一枚骄傲的小背影 2018-05-22 02:15:40

    离开你我才找回自己那爱笑的眼睛

既来之,说两句吧!

关于我

莫失莫忘,莫惆怅,莫提前生,莫妄后生。知人,知世事,自知,知余于心,力不逮~~

1根小腿毛

浏览最多

话剧《命运之影》如何再现诺

2018-05-26

暂时没有任何描述哦~

陈冠希,一直在音乐

2018-05-26

上海国际艺术节|纪

2018-05-26

照片墙

文件下载

  • 自适应图片大小

    [ 1 ]

  • 贝壳云笔记mac版本

    [ 1 ]

  • 判断移动端设备并且跳转

    [ 1 ]

  • 简体繁体互转PHP

    [ 0 ]

  • phalcon-devto

    [ 0 ]

  • PhalconYang-P

    [ 0 ]