(NHC)NiH‐Catalyzed Regiodivergent Cross‐Hydroalkenylation of Vinyl Ethers with α‐Olefins: Syntheses of 1, 2‐ and 1, 3‐Disubstituted Allyl Ethers. (9th February 2018)

• Record Type: Journal Article
• Authors: Chen, Weihao; Li, Yang; Chen, Yang; Ho, Chun‐Yu
• Is Part Of: Angewandte Chemie. Volume 130:Number 10(2018)
• Page Start: 2707
• Page End: 2711
• Publication Date: 2018-02-09
• Subjects: Allylverbindungen -- Elektronische Effekte -- Ether -- N-heterocyclische Carbene -- Nickel; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201712693
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Cross‐hydroalkenylation of a vinyl ether (1 ) with an α‐olefin (2 ) was first achieved by a set of [NHC‐Ni(allyl)]BAr F (NHC=N‐heterocyclic carbene) catalysts. Both 1, 2‐ and 1, 3‐disubstituted allyl ethers were obtained, highly selectively, by using NHCs of different sizes. In contrast, the chemoselectivity (i.e., 1 as acceptor and2 as donor) was controlled mostly by electronic effects through the catalyst–substrate interaction. Sterically bulkier alkenes (2 ) were used as preferred donors compared to smaller alkenes. This electronic effect also served as a basis for the first tail‐to‐head cross‐hydroalkenylations of1 with either a vinyl silane or boronic ester.