Development of a General Method for the Hiyama-Denmark Cross-Coupling of Tetrasubstituted Vinyl Silanes.
Development of a General Method for the Hiyama-Denmark Cross-Coupling of Tetrasubstituted Vinyl Silanes.
复制标题
DOI：
10.1021/acscatal.2c03981
复制
发表时间：
2022-10-21
期刊：
影响因子：
12.9
通讯作者：
Watson, Donald A.
中科院分区：
文献类型：
--
作者：
Pawley, Sarah B.;Conner, Allyssa M.;Omer, Humair M.;Watson, Donald A.
报道了四取代乙烯基硅烷和芳基卤化物的Hiyama-Denmark交叉偶联反应的一般条件。先前关于Hiyama-Denmark四取代乙烯基硅烷反应的报告要求使用乙烯基硅烷醇或硅烷酸酯，这很难处理，或者内部活化的乙烯基硅烷，缺乏结构通用性。现在，非活化的四取代乙烯基硅烷，具有稳定的四有机硅中心，和芳基卤化物可以偶联。这一发现的关键是鉴定了二甲基（5-甲基呋喃基）乙烯基硅烷作为实验稳定和容易制备的交叉偶联伙伴，在温和条件下易于在Hiyama-Denmark偶联中激活。这些钯催化的交叉偶联在芳酰氯中进行得很好，尽管芳酰溴和碘化物也可以耐受，并且反应在四取代烯烃的形成中显示出很高的立体特异性。此外，只需要温和的碱（KOSiMe3）和普通溶剂（THF/DMA），不需要重要的有毒添加剂（如18-crown-6）。我们还表明，这些条件同样适用于三取代乙烯基硅烷的hiyama - denmark偶联。
General conditions for the Hiyama-Denmark cross-coupling of tetrasubstituted vinyl silanes and aryl halides are reported. Prior reports of Hiyama-Denmark reactions of tetrasubstituted vinyl silanes have required the use of vinyl silanols or silanolates, which are challenging to handle, or internally activated vinyl silanes, which lack structural generality. Now, unactivated tetrasubstituted vinyl silanes, bearing bench-stable tetraorganosilicon centers, and aryl halides can be coupled. The key to this discovery is the identification of dimethyl(5-methylfuryl)vinylsilanes as bench stable and easily prepared cross-coupling partners that are readily activated under mild conditions in Hiyama-Denmark couplings. These palladium-catalyzed cross-couplings proceed well with aryl chlorides, though aryl bromides and iodides are also tolerated, and the reactions display high stereospecificity in the formation of tetrasubstituted alkenes. In addition, only a mild base (KOSiMe3) and common solvents (THF/DMA) are required, and importantly toxic additives (such as 18-crown-6) are not needed. We also show that these conditions are equally applicable to Hiyama-Denamrk coupling of trisubstituted vinyl silanes.
登录
查看更多内容
DOI：
10.3390/molecules200916892
发表时间：
2015-09-16
期刊：
Molecules (Basel, Switzerland)
影响因子：
--
作者：
Choudhury PP;Welker ME
通讯作者：
Welker ME
影响因子：
15
作者：
Denmark, SE;Tymonko, SA
通讯作者：
Tymonko, SA
影响因子：
15
作者：
Denmark, SE;Sweis, RF
通讯作者：
Sweis, RF
影响因子：
4.9
作者：
Daini, Masaki;Suginome, Michinori
通讯作者：
Suginome, Michinori
影响因子：
12.9
作者：
Bidal, Yannick D.;Lazreg, Faima;Cazin, Catherine S. J.
通讯作者：
Cazin, Catherine S. J.