Rhodium-Catalyzed Enantioselective Intramolecular Hydroacylation of Trisubstituted Alkenes

Kirsten F Johnson; Eugene A Schneider; Brian P Schumacher; Arkady Ellern; Joseph D Scanlon; Levi M Stanley

doi:10.1002/chem.201603880

Rhodium-Catalyzed Enantioselective Intramolecular Hydroacylation of Trisubstituted Alkenes

Chemistry. 2016 Oct 24;22(44):15619-15623. doi: 10.1002/chem.201603880. Epub 2016 Sep 26.

Authors

Kirsten F Johnson¹, Eugene A Schneider², Brian P Schumacher^{2

1}, Arkady Ellern¹, Joseph D Scanlon³, Levi M Stanley⁴

Affiliations

¹ Department of Chemistry, Iowa State University, Ames, IA, 50010, USA.
² Department of Chemistry, Ripon College, Ripon, WI, 54971, USA.
³ Department of Chemistry, Ripon College, Ripon, WI, 54971, USA. scanlonj@ripon.edu.
⁴ Department of Chemistry, Iowa State University, Ames, IA, 50010, USA. lstanley@iastate.edu.

PMID: 27572933
DOI: 10.1002/chem.201603880

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).

Keywords: alkenes; asymmetric catalysis; hydroacylation; rhodium.