Divergent stereocontrol of acid catalyzed intramolecular aldol reactions of 2,3,7-triketoesters: synthesis of highly functionalized cyclopentanones.
The intramolecular acid catalyzed aldol cyclization of 2,3,7-triketoesters formed from ζ-keto-α-diazo-β-ketoesters provides highly functionalized cyclopentanones with good diastereoselectivity in high overall yields via kinetically controlled and stereodivergent catalytic processes. Lewis acid catalysis gives high selectivity for the 1,2-anti tetrasubstituted cyclopentanones, whereas Brønsted acid catalysis produces the corresponding 1,2-syn diastereomer.
Department of Chemistry & Biochemistry, University of Maryland, College Park, Maryland 20742, United States.
Phong
P
Truong
Charles S
CS
Shanahan
Michael P
MP
Doyle
D000447:Aldehydes / Q000737:chemistry*; D002384:Catalysis; D003517:Cyclopentanes / Q000737:chemistry*; D004952:Esters; D007659:Ketones / Q000737:chemistry*; D058116:Lewis Acids / Q000737:chemistry*; D015394:Molecular Structure; D013237:Stereoisomerism
D000447:Aldehydes; D003517:Cyclopentanes; D004952:Esters; D007659:Ketones; D058116:Lewis Acids; C007201:cyclopentanone