162871-68-3Relevant academic research and scientific papers
Evaluation of 2-bromocyclohexenone acetals as vehicles for the introduction of C-7 oxygen preliminary to the synthesis of taxane diterpenes
Paquette,Su,Bailey,Montgomery
, p. 897 - 902 (2007/10/02)
The coupling of an optically pure, camphor-derived, β,γ-unsaturated, bicyclic ketone with a suitable vinyl organometallic is recognized to result in 1,2-addition from the endo face. Anionic oxy-Cope rearrangement of these carbinols proceeds via an 'endo-c
Stereocontrolled Oxygenation of Camphor Derivatives as a Prelude to the Complete β-Ring Functionalization of Potential Precursors to Taxol and Structural Analogs Thereof
Elmore, Steven W.,Paquette, Leo A.
, p. 889 - 896 (2007/10/02)
The possibility of realizing the predominant exo α-hydroxylation of camphor-related ketones is described.Both the direct oxidation of enolate anions with 1-phenyl-N-(phenylsulfonyl)oxaziridine or exposure of the derived silyl enol ethers to dimethyl dioxirane are conducive to exo attack.Following conversion to MOM derivatives, the acidity of the α-carbonyl proton is reduced sufficiently to allow direct condensation of these hindered ketones with cyclohexenyllithium reagents.The subsequent anionic oxy-Cope rearrangement of the resulting exo carbinols results in direct conversion to tricyclic products that feature the characteristic C-2,C-9,C-10 B-ring oxygenation pattern resident in taxol.Further, the stereogenic centers are introduced in their proper absolute configuration.The steric demands of the sigmatropic shift are discussed and the stereochemical features conducive to the minimization of steric compression subjected to experimental verification.
