Direct Enantio‐ and Diastereoselective Oxidative Homocoupling of Aldehydes
Chemistry - A European Journal
Density functional calculations, Hammett analysis, Organocatalysis, Oxidative coupling of aldehydes, Pyrrolidines
A novel strategy for the direct enantioselective oxidative homocoupling of α‐branched aldehydes is presented. The methodology employs open‐shell intermediates for the construction of chiral 1,4‐dialdehydes by forming a carbon–carbon bond connecting two quaternary stereogenic centers in good yields and excellent stereoselectivities for electron‐rich aromatic aldehydes. The 1,4‐dialdehydes were transformed into synthetically valuable chiral pyrrolidines. Experimental mechanistic investigations based on competition experiments combined with computational studies indicate that the reaction proceeds through a radical cation intermediate and that reactivity and stereoselectivity follow different trends.
Næsborg, L., Leth, L. A., Reyes-Rodriguez, G. J., Palazzo, T. A., Corti, V., & Jørgensen, K. A. (2018). Direct Enantio‐ and Diastereoselective Oxidative Homocoupling of Aldehydes. Chemistry - A European Journal, 24, (55), 14844 - 14848. https://doi.org/10.1002/chem.201803506. Retrieved from https://nsuworks.nova.edu/cnso_chemphys_facarticles/261