gem-Difluoroallylation of Aryl Halides and Pseudo Halides with Difluoroallylboron Reagents in High Regioselectivity
gem-Difluoroallylation of Aryl Halides and Pseudo Halides with Difluoroallylboron Reagents in High Regioselectivity
复制标题
高区域选择性二氟烯丙基硼试剂对芳基卤化物和拟卤化物进行偕二氟烯丙基化
DOI：
10.1002/anie.202111476
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发表时间：
2021
影响因子：
--
通讯作者：
Hartwig, John F.
中科院分区：
文献类型：
--
作者：
Sakamoto, Shu;Butcher, Trevor W.;Yang, Jonathan L.;Hartwig, John F.
我们报道了钯催化的芳基卤化物和拟卤化物与3，3-二氟烯丙基硼酸酯的高产率和高区域选择性的二氟烯丙基化反应，并报道了廉价的气态3，3，3-三氟丙烯与双(频那多)二硼在铜催化下的脱氟硼化反应。芳基和杂芳基溴化物的GEM-二氟烯丙基化反应只需很低的催化剂负载量(0.1mol %[Pd])，并能容忍多种官能团，包括伯醇、仲胺、醚、酮、酯、酰胺、醛、腈、卤化物和硝基。该方案扩展到芳基碘化物、氯化物和三氟化物，以及取代的二氟烯丙基硼酸酯，提供了一种通用的二氟烯丙基芳烃的合成方法，我们证明这些芳烃是一系列氟化构筑块的有价值的中间体。
We report the palladium‐catalyzedgem‐difluoroallylation of aryl halides and pseudo halides with 3,3‐difluoroallyl boronates in high yield with high regioselectivity, and we report the preparation of the 3,3‐difluoroallyl boronate reactants by a copper‐catalyzed defluorinative borylation of inexpensive gaseous 3,3,3‐trifluoropropene with bis(pinacolato)diboron. Thegem‐difluoroallylation of aryl and heteroaryl bromides proceeds with low catalyst loading (0.1 mol % [Pd]) and tolerates a wide range of functional groups, including primary alcohols, secondary amines, ethers, ketones, esters, amides, aldehydes, nitriles, halides, and nitro groups. This protocol extends to aryl iodides, chlorides, and triflates, as well as substituted difluoroallyl boronates, providing a versatile synthesis ofgem‐difluoroallyl arenes that we show to be valuable intermediates to a series of fluorinated building blocks.