Deacylative oxidation strategy for the preparation of alpha-functionalized carbonyls.
[reaction: see text] alpha-Alkoxylation and amination of carbonyl derivatives is made possible through a unique deacylative coupling reaction that proceeds via in situ Rh-carbene formation and subsequent heteroatom-H (X-H) insertion. Reactions perform optimally with five- and six-membered ring lactone and lactam derivatives using both alcohol and carbamate substrates as coupling partners. Substituted ethylbenzoyl acetate starting materials have also proven to be effective for this oxidative process, affording alpha-functionalized esters under particularly mild and operationally facile conditions.
Brodsky
Benjamin H
BH
Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA.
Du Bois
J
J
D002384:Catalysis; D007202:Indicators and Reagents; D007659:Ketones / Q000138:chemical synthesis*; D007769:Lactams / Q000737:chemistry*; D007783:Lactones / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction
D007202:Indicators and Reagents; D007659:Ketones; D007769:Lactams; D007783:Lactones