Rhodium-Catalyzed Pauson-Khand Reaction Using a Small-Bite- Angle P-Stereogenic C1-Diphosphine Ligand

Article

Authorship

Cristóbal Lecina, Edgar ; COSTANTINO, ANDREA ROSANA ; Grabulosa, Arnald ; Riera, Antoni ; Verdaguer, Xavier

Date

2015

Publishing House and Editing Place

American Chemical Society

Magazine

ORGANOMETALLICS, vol. 34 (pp. 4989-4993) American Chemical Society

Summary Information provided by the agent in SIGEVA

The asymmetric Pauson–Khand reaction catalyzed by [Rh(COD)(MaxPHOS)]BF4 is described. Several 1,6-enynes have been chosen as model substrates affording moderate yields and selectivities of up to 86% ee. Besides binap-type ligands, we have demonstrated that the P-stereogenic C1-symmetry small-bite-angle ligand MaxPHOS is a viable ligand in this process. The formation of [2+2+2] cycloaddition compounds has shown to be a competitive process. A mechanism is proposed to account for the observe... The asymmetric Pauson–Khand reaction catalyzed by [Rh(COD)(MaxPHOS)]BF4 is described. Several 1,6-enynes have been chosen as model substrates affording moderate yields and selectivities of up to 86% ee. Besides binap-type ligands, we have demonstrated that the P-stereogenic C1-symmetry small-bite-angle ligand MaxPHOS is a viable ligand in this process. The formation of [2+2+2] cycloaddition compounds has shown to be a competitive process. A mechanism is proposed to account for the observed results. The intermediate rhodium dicarbonyl complex 6 was synthesized, and its solid-state structure was elucidated by X-ray crystallography.