Felix, Ryan J.; Weber, Dieter; Gutierrez, Osvaldo; Tantillo, Dean J.; Gagne, Michel R. published the artcile< A gold-catalysed enantioselective Cope rearrangement of achiral 1,5-dienes>, Computed Properties of 325168-88-5, the main research area is gold catalysis enantioselective cope rearrangement achiral dienes.
Since the discovery of the Cope rearrangement in the 1940s, no asym. variant of the rearrangement of achiral 1,5-dienes has emerged, despite the successes that have been achieved with its heteroatom variants (Claisen, aza-Cope, and so on). This article reports the first example of an enantioselective Cope reaction that starts from an achiral diene. The new gold(I) catalyst derived from double Cl–abstraction of ((S)-3,5-xylyl-PHANEPHOS(AuCl)2), has been developed for the sigmatropic rearrangement of alkenyl-methylenecyclopropanes. The reaction proceeds at low temperature and the synthetically useful vinylcyclopropane products are obtained in high yield and enantioselectivity. D. functional theory calculations predict that: (1) the reaction proceeds via a cyclic carbenium ion intermediate, (2) the relief of strain in the methylenecyclopropane moiety provides the thermodn. driving force for the rearrangement and (3) metal complexation of the transition-state structure lowers the rearrangement barriers.
Nature Chemistry published new progress about [3,3]-Sigmatropic rearrangement. 325168-88-5 belongs to class chiral-phosphine-ligands, and the molecular formula is C48H50P2, Computed Properties of 325168-88-5.
Referemce:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate