664987-26-2Relevant academic research and scientific papers
Fluoride ion-promoted α-ketol rearrangement during unmasking of silyl-protected medium-ring dihydroxy ketones
Hartung, Ryan E.,Hilmey, David G.,Paquette, Leo A.
, p. 713 - 716 (2004)
A new strategy for implementing α-ketol rearrangements under mild conditions is presented. The reactants are mono- and disilylated stereoisomers of α,α′- and α,β-dihydroxycycloheptanones and -cyclooctanones. Compounds of this class experience ready deprotection upon treatment with tetrabutyl-ammonium fluoride. In certain examples, this process is accompanied by structural isomerization. Since the product diols are stable to the reaction conditions, these chemical changes have been attributed to kinetically controlled events following transient alkoxide generation resulting from cleavage of the O-Si bond proximal to the carbonyl group. The experimental findings are evaluated against a backdrop of calculated (MM3) steric energies of the silicon-free products and their response to equilibration under strongly basic conditions.
Synthesis of Stereoisomeric Medium-Ring α,α′-Dihydroxy Cycloalkanones
Paquette, Leo A.,Hartung, Ryan E.,Hofferberth, John E.,Vilotijevic, Ivan,Yang, Jiong
, p. 2454 - 2460 (2007/10/03)
The stereochemical course of the epoxidation of the silyl enol ethers of 2-tert-butyldimethylsilyl-oxycycloheptanone and -cyclooctanone has been investigated and shown to proceed exclusively anti to the existing α-substituent. 2-(Benzyloxy)cyclooctanone b
Chemical consequences of the ground-state conformations of cyclooctyl rings. Examples of reactivity differences in α-hydroxy and α,α′-dihydroxy eight-membered cyclic ketones
Paquette, Leo A.,Hartung, Ryan
, p. 1201 - 1208 (2007/10/03)
A program directed toward the elucidation of various conformational factors that control reactivity differences in cyclooctyl and cyclooctenyl systems is described. This overview reports on the divergent reactivity observed in the alkylation of saturated
