Univ Rennes, CNRS, ISCR UMR 6226, F-35000 Rennes, France.
Org Lett. 2020 Aug 7;22(15):5936-5940. doi: 10.1021/acs.orglett.0c02023. Epub 2020 Jul 9.
We report herein P(III)-directed C-H bond alkenylation of (dialkyl)- and (diaryl)biarylphosphines using internal alkynes. Chloride-free [Rh(OAc)(COD)] acts as a better catalyst than commercially available [RhCl(COD)]. Conditions were developed to control the mono- and difunctionalization depending on the alkyne stoichiometry. One of these novel bisalkenylated (dialkyl)biarylphosphines was employed for the preparation of a palladium(II) complex, and some of these functionalized ligands outperformed their corresponding unfunctionalized phosphines in Pd-catalyzed amidation with sterically hindered aryl chlorides.
我们在此报告使用内炔烃对（二烷基）和（二芳基）联苯膦进行 P(III)-导向的 C-H 键烯基化反应。无氯化物的[Rh(OAc)(COD)]比市售的[RhCl(COD)]表现出更好的催化性能。根据炔烃的化学计量比，开发了条件来控制单官能化和双官能化。这些新型的双烯基化（二烷基）联苯膦中的一种被用于制备钯（II）配合物，并且这些功能化配体在钯催化的具有空间位阻的芳基氯化物的酰胺化反应中优于其相应的未功能化的膦。
