Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2015 Apr 13;54(16):4895-8.
doi: 10.1002/anie.201411852. Epub 2015 Mar 3.

Direct catalytic enantio- and diastereoselective ketone aldol reactions of isocyanoacetates

Raquel de la Campa  1 , Irene Ortín, Darren J Dixon
Affiliations

Direct catalytic enantio- and diastereoselective ketone aldol reactions of isocyanoacetates

Raquel de la Campa et al. Angew Chem Int Ed Engl. .

Abstract

A catalytic asymmetric aldol addition/cyclization reaction of unactivated ketones with isocyanoacetate pronucleophiles has been developed. A quinine-derived aminophosphine precatalyst and silver oxide were found to be an effective binary catalyst system and promoted the reaction to afford chiral oxazolines possessing a fully substituted stereocenter with good diastereoselectivities and excellent enantioselectivities.

Keywords: aldol reaction; asymmetric catalysis; enantioselectivity; isocyanoacetates; oxazolines.

PubMed Disclaimer

Figures

scheme 1
scheme 1
a)Catalytic asymmetric addition reactions of isocyanoacetate pronucleophiles to carbonyl or imine electrophiles. b)Aminophosphine/silver(I) binary catalyst system applied in this work.
scheme 2
scheme 2
Application of the ketone aldol reaction to the formation of fused bicyclic lactams.
scheme 3
scheme 3
Synthetic manipulations of the oxazoline products.
scheme 4
scheme 4
Proposed transition-state model rationalizing the stereochemical outcome of the reaction of 3 a and 2 a in the presence of 1 a and Ag2O.
See this image and copyright information in PMC

References

    1. For reviews on asymmetric aldol reactions, see:
    1. Mahrwald R. Modern Aldol Reactions. Weinheim: Wiley-VCH; 2004.
    1. Trost BM, Brindle CS. Chem. Soc. Rev. 2010;39:1600–1632. - PMC - PubMed
    1. Palomo C, Oiarbide M, García JM. Chem. Soc. Rev. 2004;33:65–75. - PubMed
    1. Geary LM, Hultin PG. Tetrahedron: Asymmetry. 2009;20:131–173.

LinkOut - more resources