Arylative Intramolecular Allylation of Ketones with 1, 3‐Enynes Enabled by Catalytic Alkenyl‐to‐Allyl 1, 4‐Rhodium(I) Migration. Issue 25 (19th May 2017)

• Record Type: Journal Article
• Authors: Partridge, Benjamin M.; Callingham, Michael; Lewis, William; Lam, Hon Wai
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 25(2017)
• Page Start: 7227
• Page End: 7232
• Publication Date: 2017-05-19
• Subjects: allylic compounds -- cyclization -- isomerization -- reaction mechanisms -- rhodium; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201703155
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Alkenyl‐to‐allyl 1, 4‐rhodium(I) migration enables the generation of nucleophilic allylrhodium(I) species by remote C−H activation. This new mode of reactivity was employed in the diastereoselective reaction of arylboron reagents with substrates containing a 1, 3‐enyne tethered to a ketone, to give products containing three contiguous stereocenters. The products can be obtained in high enantioselectivities using a chiral sulfur‐alkene ligand. Abstract : On the move : The title migration enables the generation of nucleophilic allylrhodium(I) species by remote C−H activation. This new mode of reactivity was employed in the diastereoselective reaction of arylboron reagents with substrates containing a 1, 3‐enyne tethered to a ketone, to give products containing three contiguous stereocenters. The products can be obtained in high enantioselectivities using a chiral sulfur‐alkene ligand.