Direct catalytic enantio- and diastereoselective Mannich reaction of isocyanoacetates and ketimines

Irene Ortín; Darren J Dixon

doi:10.1002/anie.201309719

Direct catalytic enantio- and diastereoselective Mannich reaction of isocyanoacetates and ketimines

Angew Chem Int Ed Engl. 2014 Mar 24;53(13):3462-5. doi: 10.1002/anie.201309719. Epub 2014 Feb 24.

Authors

Irene Ortín¹, Darren J Dixon

Affiliation

¹ Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA (UK).

PMID: 24615896
DOI: 10.1002/anie.201309719

Abstract

A catalytic asymmetric synthesis of imidazolines with a fully substituted β-carbon atom by a Mannich-type addition/cyclization reaction of isocyanoacetate pronucleophiles and N-diphenylphosphinoyl ketimines has been developed. When a combination of a cinchona-derived aminophosphine precatalyst and silver oxide was employed as a binary catalyst system, good reactivity, high diastereoselectivities (up to 99:1 d.r.), and excellent enantioselectivities (up to 99% ee) were obtained for a range of substrates.

Keywords: Mannich reaction; asymmetric catalysis; cooperative catalysis; imidazolines; ketimines.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Catalysis
Cyclization
Imidazolines / chemistry*
Imines / chemistry*
Ketones / chemistry*
Molecular Structure
Nitriles / chemistry*
Stereoisomerism

Substances

Imidazolines
Imines
Ketones
Nitriles
ketimine