title: Rhodium-Catalyzed Enantioselective Intramolecular Hydroacylation of Trisubstituted Alkenes.
abstract: We report the first examples of transition metal-catalyzed enantioselective alkene hydroacylations with 1,1,2-trisubstituted alkenes. DFT and mechanistic studies are consistent with a reaction pathway for these rhodium-catalyzed processes including intramolecular alkene hydroacylation and α-epimerization to generate highly enantioenriched, polycyclic architectures. This reaction sequence enables the hydroacylation of 2-(cyclohex-1-en-1-yl)benzaldehydes to form hexahydro-9H-fluoren-9-ones in moderate to high yields (68-91 %) with high enantioselectivities (up to 99 % ee) and diastereoselectivities (typically >20:1).
authors: Department of Chemistry, Iowa State University, Ames, IA, 50010, USA.
authors: Kirsten F
authors: KF
authors: Johnson
authors: Department of Chemistry, Ripon College, Ripon, WI, 54971, USA.
authors: Eugene A
authors: EA
authors: Schneider
authors: Department of Chemistry, Ripon College, Ripon, WI, 54971, USA.|Department of Chemistry, Iowa State University, Ames, IA, 50010, USA.
authors: Brian P
authors: BP
authors: Schumacher
authors: Department of Chemistry, Iowa State University, Ames, IA, 50010, USA.
authors: Arkady
authors: A
authors: Ellern
authors: Department of Chemistry, Ripon College, Ripon, WI, 54971, USA. scanlonj@ripon.edu.
authors: Joseph D
authors: JD
authors: Scanlon
authors: Department of Chemistry, Iowa State University, Ames, IA, 50010, USA. lstanley@iastate.edu.
authors: Levi M
authors: http://orcid.org/0000-0001-8804-1146
authors: LM
authors: Stanley
keywords: alkenes; asymmetric catalysis; hydroacylation; rhodium