A General Palladium‐Catalyzed Hiyama Cross‐Coupling Reaction of Aryl and Heteroaryl Chlorides. Issue 19 (21st March 2016)

• Record Type: Journal Article
• Authors: Yuen, On Ying; So, Chau Ming; Man, Ho Wing; Kwong, Fuk Yee
• Is Part Of: Chemistry. Volume 22:Issue 19(2016)
• Page Start: 6471
• Page End: 6476
• Publication Date: 2016-03-21
• Subjects: aryl chlorides -- aryl(alkoxy)silane -- cross-coupling reaction -- palladium -- phosphine ligand; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201600420
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: A general palladium‐catalyzed Hiyama cross‐coupling reaction of aryl and heteroaryl chlorides with aryl and heteroaryl trialkoxysilanes by a Pd(OAc)2 /L2 catalytic system is presented. A newly developed water addition protocol can dramatically improve the product yields. The conjugation of the Pd/L2 system and the water addition protocol can efficiently catalyze a broad range of electron‐rich, ‐neutral, ‐deficient, and sterically hindered aryl chlorides and heteroaryl chlorides with excellent yields within three hours and the catalyst loading can be down to 0.05 mol % Pd for the first time. Hiyama coupling of heteroaryl chlorides with heteroaryl silanes is also reported for the first time. The reaction can be easily scaled up 200 times (100 mmol) without any degasification and purification of reactants; this facilitates the practical application in routine synthesis. Abstract : The Pd/L2 system is highly active towards the Hiyama coupling of aryl and heteroaryl chlorides. A wide range of aryl chlorides and aryl(alkoxy)silanes including sterically hindered and heterocyclic substrates can be cross‐coupled successfully. A new water addition protocol has been developed that can dramatically improve the desired product yields (see scheme).