Enolate generation under hydrogenation conditions: catalytic aldol cycloreduction of keto-enones.
[reaction: see text] Formal heterolytic activation of elemental hydrogen under Rh catalysis enables the reductive generation of enolates from enones under hydrogenation conditions. Enolates generated in this fashion participate in catalytic C-C bond formation via carbonyl addition to aldehyde and, as demonstrated in this account, ketone partners. Notably, the use of appendant dione partners enables diastereoselective formation of cycloaldol products possessing 3-stereogenic centers, including 2-contiguous quaternary centers.
Huddleston
Ryan R
RR
Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, Texas 78712, USA.
Krische
Michael J
MJ
D000447:Aldehydes / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D006571:Heterocyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry*; D006865:Hydrogenation; D007659:Ketones / Q000737:chemistry*; D015394:Molecular Structure
D000447:Aldehydes; D006571:Heterocyclic Compounds; D007659:Ketones; D006859:Hydrogen