Chemistry and Physics Faculty Articles

Title

Direct Enantio‐ and Diastereoselective Oxidative Homocoupling of Aldehydes

Document Type

Article

Publication Date

10-1-2018

Publication Title

Chemistry - A European Journal

Keywords

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

ISSN

1521-3765

Volume

24

Issue/No.

55

First Page

14844

Last Page

14848

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.

Comments

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

ORCID ID

0000-0002-0566-0820

ResearcherID

V-6501-2018

DOI

10.1002/chem.201803506

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Peer Reviewed

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