Palladium-Catalyzed Cross-Coupling Reactions of Carboranes with Alkenes via Selective B–H Bond Activation

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 17, 2025

A palladium-catalyzed Heck-type cross-coupling reaction of carboranes with alkenes in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) was realized. This shows good B(9) selectivity for m-carboranes and is also suitable o- p-carborane. Meanwhile, a series mono-, di-, trisubstituted were compatible substrates to afford the alkenylated products 16–89% yields. The 1,2-bis(carboranyl)ethylene first synthesized by vinyltrimethylsilane m-carborane. Further transformations C═C bond product examined hydroboration oxidation, hydroboration, bromination generate corresponding B(9)-functionalized m-carboranes.

Language: Английский

Palladium-Catalyzed ortho C–H Allylation of Tertiary Anilines

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 26, 2025

Allyl groups could be transformed into various functional groups. A novel and highly regioselective approach for the Pd-catalyzed ortho C–H allylation of tertiary anilines has been developed. Various substitution were well-tolerated, allylated linezolid, ibuprofen, naproxen, ketoprofen, dehydroabietic acid derivatives easily prepared. Notably, this new method overcomes limitations classical amide-directing groups, as amide are well-tolerated in reaction. Preliminary mechanistic studies revealed that a dual-ligand effect may involved achieving excellent selectivity reaction facilitated by N-Bz-Gly Ag2CO3. Further indicate FeCl3 is necessary Lewis to activate allyl bromide.

Language: Английский