Regio- and stereochemically controlled formation of hydroxamic acid containing anti- or syn-1,4-cycloalkenols from acylnitroso-derived Diels-Alder adducts.
Treatment of acylnitroso hetero Diels-Alder cycloadducts 2 with iron(III) or copper(II) in an alcohol solvent induces ring opening to afford predominantly monocyclic anti-1,4-hydroxamic acids 3. However, treatment of cycloadducts 2 with copper(II) in toluene reverses the stereoselectivity of the ring opening to afford syn-1,4-hydroxamic acids 4. These regio- and stereoselective processes separately provide anti-1,4- and syn-1,4-disubstituted cyclopentenes while regenerating a hydroxamic acid moiety, thus enhancing the chemical versatility of the Diels-Alder cycloadducts.
Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, USA.
M D
MD
Surman
M J
MJ
Miller
D003300:Copper / Q000737:chemistry; D003516:Cycloparaffins / Q000737:chemistry*; D005290:Ferric Compounds / Q000737:chemistry; D006877:Hydroxamic Acids / Q000138:chemical synthesis*; D009603:Nitroso Compounds / Q000737:chemistry*; D013237:Stereoisomerism
D003516:Cycloparaffins; D005290:Ferric Compounds; D006877:Hydroxamic Acids; D009603:Nitroso Compounds; D003300:Copper; C029892:cupric chloride