Direct Enantio‐ and Diastereoselective Oxidative Homocoupling of Aldehydes

Authors

Line Næsborg, Aarhus University - Denmark
Lars A. Leth, Aarhus University - Denmark
Gabriel J. Reyes-Rodriguez, Aarhus University - DenmarkFollow
Teresa A. Palazzo, Aarhus University - Denmark
Vasco Corti, Aarhus University - Denmark
Karl Anker Jørgensen, Aarhus University - Denmark

ORCID

0000-0002-0566-0820

ResearcherID

V-6501-2018

Document Type

Article

Publication Title

Chemistry - A European Journal

ISSN

1521-3765

Publication Date

10-1-2018

Keywords

Density functional calculations, Hammett analysis, Organocatalysis, Oxidative coupling of aldehydes, Pyrrolidines

Abstract

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.

DOI

10.1002/chem.201803506

Volume

24

Issue

55

First Page

14844

Last Page

14848

Comments

©2018 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim

NSUWorks Citation

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