上海
Glaser偶聯(lián)是通過兩個端基炔合成對稱二炔或環(huán)狀二炔的常用反應(yīng)。機理上與Eglinton 反應(yīng)類似，不同的是此反應(yīng)用一價銅作為催化劑，通過反應(yīng)中加入氧氣重新氧化完成催化循環(huán)。
與之類似的Hay偶聯(lián)相比Glaser偶聯(lián)有很多優(yōu)點，此反應(yīng)中用到的Cu-TMEDA絡(luò)合物催化劑可以溶于很多溶劑，所以反應(yīng)應(yīng)用性更廣。
Cadiot-Chodkiewicz 偶聯(lián)可以合成非對稱的二炔可以作為此反應(yīng)的互補反應(yīng)，很有價值。
反應(yīng)機理
圖片來源：https://cheminfographic.wordpress.com/2018/02/18/74-glaser-hay-coupling-1869/
反應(yīng)實例
Efficient Copper(II) Acetate Catalyzed Homo- and Heterocoupling of Terminal Alkynes at Ambient Conditions
K. Balaraman, V. Kesavan, Synthesis, 2010, 3461-3466.
Phase Separation As a Strategy Toward Controlling Dilution Effects in Macrocyclic Glaser-Hay Couplings
A.-C. Bédard, S. K. Collins, J. Am. Chem. Soc., 2011, 133, 19976-19981.
One-Pot Formation and Derivatization of Di- and Triynes Based on the Fritsch-Buttenberg-Wiechell Rearrangement
T. Luu, Y. Morisaki, N. Cunningham, R. R. Tykwinski, J. Org. Chem., 2007, 72, 9622-9629.
End-Cap Stabilized Oligoynes: Model Compounds for the Linear sp Carbon Allotrope Carbyne
T. Gibtner, F. Hampel, J.-P.Gisselbrecht, A. Hirsch, Chem. Eur. J., 2002, 68, 408-432.
L. Su, J. Dong, L. Liu, M. Sun, R. Qiu, Y. Zhou, S.-F. Yin, J. Am. Chem. Soc., 2016, 138, 12348-12351.
參考資料
Organic Chemistry Portal：Glaser Coupling、Hay Coupling
特別聲明：以上內(nèi)容(如有圖片或視頻亦包括在內(nèi))為自媒體平臺“網(wǎng)易號”用戶上傳并發(fā)布，本平臺僅提供信息存儲服務(wù)。
Notice: The content above (including the pictures and videos if any) is uploaded and posted by a user of NetEase Hao, which is a social media platform and only provides information storage services.
