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三氯苯基甲酸酯:高反应性且易于获得的结晶 CO 替代物,用于钯催化的芳基/烯基卤化物和三氟甲磺酸酯的羰基化反应。

Trichlorophenyl formate: highly reactive and easily accessible crystalline CO surrogate for palladium-catalyzed carbonylation of aryl/alkenyl halides and triflates.

机构信息

School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Shizuoka 422-8526, Japan.

出版信息

Org Lett. 2012 Oct 19;14(20):5370-3. doi: 10.1021/ol302593z. Epub 2012 Sep 28.

Abstract

The high utility of 2,4,6-trichlorophenyl formate, a highly reactive and easily accessible crystalline CO surrogate, is demonstrated. The decarbonylation with NEt(3) to generate CO proceeded rapidly at rt, thereby allowing external-CO-free Pd-catalyzed carbonylation of aryl/alkenyl halides and triflates. The high reactivity of the CO surrogate enabled carbonylation at rt and significantly reduced the quantities of formate to near-stoichiometric levels. The obtained trichlorophenyl esters can be readily converted to a variety of carboxylic acid derivatives in high yields.

摘要

高反应性且易于获得的结晶态 CO 替代物 2,4,6-三氯苯基甲酸酯的高实用性得到了证明。与 NEt(3) 脱羰生成 CO 可在室温下迅速进行,从而实现了无外部 CO 的芳基/烯基卤化物和三氟甲磺酸酯的 Pd 催化羰基化反应。CO 替代物的高反应活性使得室温下的羰基化反应成为可能,并显著减少了甲酸盐的用量至接近化学计量比。得到的三氯苯基酯可很容易地以高产率转化为各种羧酸衍生物。

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