Laboratory of Organic Chemistry, ETH Zurich, Vladimir-Prelog-Weg 3, 8093, Zurich, Switzerland.
Eli Lilly and Company, Indianapolis, IN, 46285, USA.
Angew Chem Int Ed Engl. 2021 Feb 19;60(8):3918-3922. doi: 10.1002/anie.202014581. Epub 2020 Dec 22.
We report the synthesis of potassium acyltrifluoroborates (KATs) by a palladium-catalyzed cross-coupling of boronic acids and the thioimidate KAT transfer reagent. The combination of widely available aryl- and vinylboronic acids with commercially available thioimidate 1 using catalytic Pd and a Cu additive enables the preparation of KATs in high yields and with good functional group tolerance. This formal insertion of CO into organoboronic acids can also be applied to boronic acid pinacol esters and potassium organotrifluoroborates using a slightly modified procedure. The cross-coupling can be telescoped into the one-pot synthesis of amides and α-aminotrifluoroborates by exploiting the unique chemistry of KATs and their trifluoroborate iminium (TIM) derivatives.
我们报告了通过钯催化硼酸与硫代亚胺 KAT 转移试剂的交叉偶联合成钾酰基三氟硼酸盐 (KATs)。使用催化 Pd 和 Cu 添加剂，将广泛可用的芳基和乙烯基硼酸与商业上可用的硫代亚胺 1 结合，可在高产率和良好的官能团耐受性下制备 KATs。这种将 CO 正式插入有机硼酸中的方法也可以通过稍微修改的程序应用于硼酸频哪醇酯和钾有机三氟硼酸盐。通过利用 KATs 和其三氟硼酸盐亚胺 (TIM) 衍生物的独特化学性质，可以将交叉偶联缩合到酰胺和 α-氨基三氟硼酸盐的一锅合成中。
