Kakusawa Naoki, Kurita Jyoji
Faculty of Pharmaceutical Sciences, Hokuriku University, Kanagawa-machi, Kanazawa 920-1181, Japan.
Chem Pharm Bull (Tokyo). 2006 May;54(5):699-702. doi: 10.1248/cpb.54.699.
Palladium-catalyzed carbonylative cross-coupling reaction of ethynylstibane (PhSbPh(2)) and aryl iodides (Ar-I) is described. The reaction of the stibanes and the halides under 1 atm of carbon monoxide in N,N-dimethylacetamide using a combination of 5 mol% Pd(OAc)(2) and 4 equivalents (20 mol%) of PPh(3) brought about carbonylative cross-coupling reaction to afford arylethynylketones [ArC(O)Ph] in good yields along with a small amount of directly coupled products, aryl acetylens (ArPh). Formation of the side product was completely suppressed by conducting the reaction under high CO pressure (20 atm) conditions. The present method provides a variety of carbonylated products in good yield even with electron-deficient aryl iodides which usually give inferior results due to their tendency to undergo decarbonylation in the cross-coupling reaction of ethynylstibanes and acyl halides.
描述了钯催化乙炔基锑（PhSbPh(2)）与芳基碘化物（Ar-I）的羰基化交叉偶联反应。在N，N-二甲基乙酰胺中，在1个大气压的一氧化碳下，使用5 mol%的Pd(OAc)(2)和4当量（20 mol%）的三苯基膦的组合，使锑化物与卤化物发生反应，实现羰基化交叉偶联反应，以良好的产率得到芳基乙炔基酮[ArC(O)Ph]，同时伴有少量直接偶联产物芳基乙炔（ArPh）。通过在高CO压力（20个大气压）条件下进行反应，可完全抑制副产物的形成。即使对于缺电子的芳基碘化物，本方法也能以良好的产率提供各种羰基化产物，这些缺电子芳基碘化物由于在乙炔基锑与酰卤的交叉偶联反应中易于脱羰，通常会得到较差的结果。
