New Hindered Amide Base for Aryne Insertion into Si–P, Si–S, Si–N, and C–C Bonds
Year: 2018
Type: article
Abstract: A general method for a new, hindered lithium diadamantylamide (LDAM) base-promoted insertion of arynes into Si-P, Si-S, Si-N, and C-C bonds is described. Arynes are generated from easily available aryl triflates and halides. Subsequent reaction of the aryne with silylated phosphines, sulfides, or amines affords the insertion products. Furthermore, a one-step synthesis of anthracenes from aryl halides and aryl ketones is also demonstrated. Cyano, aryl, alkyl, trifluoromethyl, vinyl, methoxy, chloro, fluoro, and even formyl moieties are compatible with the reaction conditions. The new lithium amide affords higher yields compared with lithium tetramethylpiperidide (LiTMP)-promoted reactions. Furthermore, the bulkiness of LDAM base essentially suppresses aryne reaction with base, allowing use of aryl halides and triflates as the limiting reagents.
DOI: 10.1021/jacs.8b07064
Authors: Milad Mesgar, Justin Nguyen-Le, Olafs Daugulis
Institution: University of Houston
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W2896128973