Highly Diastereoselective Michael Reactions Using β-Nitrocarbonyl Nucleophiles.
We have discovered a highly diastereoselective Michael reaction of α-substituted, β-nitrocarbonyl compounds to deliver highly functionalized stereodiads containing fully substituted nitrogen-bearing centers. Good to excellent yields and diastereoselectivities are observed. This transformation is tolerant of various types of carbonyl groups on the nucleophilic partner, as well as a range of unsaturated electrophiles. Mechanistic investigations are consistent with internal hydrogen bonding in the nitroalkane tautomer as the major factor in the control of diastereoselectivity in these transformations.
Department of Chemistry and Biochemistry, University of Delaware , Newark, Delaware 19716, United States.
Amber A S
AA
Gietter-Burch
Department of Chemistry and Biochemistry, University of Delaware , Newark, Delaware 19716, United States.
Roxana E
RE
Mitrut
Department of Chemistry and Biochemistry, University of Delaware , Newark, Delaware 19716, United States.
Donald A
DA
Watson
D002384:Catalysis; D004952:Esters; D006860:Hydrogen Bonding; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry*; D015394:Molecular Structure; D009574:Nitro Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D009584:Nitrogen / Q000737:chemistry; D013237:Stereoisomerism
D004952:Esters; D007659:Ketones; D009574:Nitro Compounds; D009584:Nitrogen