Download PDF
Synfacts 2025; 21(01): 38
DOI: 10.1055/a-2467-5324
Metals in Synthesis

Asymmetric Semipinacol Rearrangement of Diarylallylic Alcohols to α-Aryl Ketones under Cobalt Catalysis

Contributor(s):
Martin Oestreich 
,
Hendrik F. T. Klare 
,
Phillip Pommerening 
Kalomenopoulos PG, Emayavaramban B, Johnston CP *. University of St Andrews, UK
Enantioselective Synthesis of α-Aryl Ketones by a Cobalt-Catalyzed Semipinacol Rearrangement.

Angew. Chem. Int. Ed. 2024;
DOI: 10.1002/anie.202414342
CrossrefPubMedSearch in Google Scholar
› Further Information
 
 PDF Download Permissions and Reprints

Keywords

α-aryl ketones - asymmetric catalysis - cobalt catalysis - phenonium ions - semipinacol rearrangement

Significance

Johnston and co-workers report the enantioselective synthesis of α-aryl ketones from α,α-diarylallylic alcohols by a chiral cobalt–salen-catalyzed semipinacol rearrangement. A racemic photocatalyzed protocol has been reported recently by Lindner and Carreira (Angew. Chem. Int. Ed. 2024, 63, e202407827).


#

Comment

While the α-aryl ketones are obtained in excellent enantioselectivities with para- and meta-substituted substrates, the stereoselectivity decreases drastically with substituents in the ortho-position. For two different aryl substituents, a Hammett analysis revealed the preferred migration of the more electron-rich aryl group. 


#
#

Publication History

Article published online:
20 December 2024

© 2024. Thieme. All rights reserved.

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


   Permissions and Reprints