Download PDF
Synfacts 2025; 21(07): 700
DOI: 10.1055/a-2601-5444
Metals in Synthesis

Directing-Group-Enabled Palladium-Catalyzed Reverse Regioselective Dicarbofunctionalization of Acrylamides

Contributor(s):
Mark Lautens 
,
Justin Ching
Suzuki H, Moro R, Matsuda T *. University of Fukui and Tokyo University of Science, Japan
Reverse Regioselective Dicarbofunctionalization via Anti-Michael-Type Addition.

Angew. Chem. Int. Ed. 2025;
DOI: 10.1002/anie.202505391
CrossrefPubMedSearch in Google Scholar
› Further Information
 
 PDF Download Permissions and Reprints

Keywords

palladium catalysis - directing group - anti-Michael addition

Significance

Suzuki and co-workers report a reverse regioselective dicarbofunctionalization of acrylamides. The use of N-(quinolin-8-yl)acrylamide (AQ) as a directing group was crucial for the reversal in regioselectivity observed. The reaction is proposed to proceed through a Pd-catalyzed anti-Michael-type addition, followed by oxidative addition of the electrophile, and reductive elimination to generate the desired product.


#

Comment

The authors were able to isolate the alkyl-PdII intermediate A and subject it to the reaction conditions. Stoichiometric amounts of the alkyl-PdII intermediate A delivered the product in 54 % yield. When Pd(OAc)2 was replaced with the same intermediate, the product was generated in 65 % yield. Taken altogether, the alkyl-PdII species is likely formed en route towards the product.


#
#

Publication History

Article published online:
23 June 2025

© 2025. Thieme. All rights reserved.

Georg Thieme Verlag KG
Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany


   Permissions and Reprints