Chiral Concave N-Heterocyclic Carbenes 3 rd International Summer School “Supramolecular Systems in Chemistry and Biology“ Tim Reimers Kiel, GER.

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Presentation transcript:

Chiral Concave N-Heterocyclic Carbenes 3 rd International Summer School “Supramolecular Systems in Chemistry and Biology“ Tim Reimers Kiel, GER

N-Heterocyclic Carbenes (NHC) Different ring sizes… Different heteroatoms… Bulky groups R are needed to avoid dimerization

How to make NHCs? E.g. by deprotonation: First crystalline carbene (1991)! A. J. Arduengo III, R. L. Harlow, M. Kline, J. Am. Chem. Soc. 1991, 113, 361. Ad = Adamantyl

What can NHCs be used for? As ligands in transition metal mediated reactions: Olefin metathesis Suzuki-Miyaura reaction M. Scholl, S. Ding, C. W. Lee, R. H. Grubbs, Org. Lett. 1999, 6, 953. O. Navarro, R. A. Kelly III, S. P. Nolan, J. Am. Chem. Soc. 2003, 125,

What can NHCs be used for? As organocatalysts: C. Burstein, F. Glorius, Angew. Chem. Int. Ed. 2004, 43, 6205.

What does “concave“ mean?

A Concave Catalyst Concave system Reactive centre

A ConcaveCatalyst Concave system Reactive centre Solvent Substrate Functional group

Turn over number? A ConcaveCatalyst

Concave bimacrocyclic NHC

Special Effect with a Concave NHC 52 % X = (CH 2 ) 8 41 % X = (CH 2 ) 10 3 % n. o. 42 % O. Winkelmann, C. Näther, U. Lüning, Org. Biomol. Chem. 2009, 7, 553. ****

Chiral Concave NHC

Problem: Interconversion by rotation at room temperature Chiral resolution impossible!

NMR Experiments O. Winkelmann, D. Linder, J. Lacour, C. Näther, U. Lüning, Eur. J. Org. Chem. 2007,

NMR Experiments CDCl 3 C 2 D 2 Cl 4 CD 2 Cl 2 C 2 D 2 Cl 2 d.e. 40 % d.e. 17 % d.e. 15 % d.e. 10 % O. Winkelmann, D. Linder, J. Lacour, C. Näther, U. Lüning, Eur. J. Org. Chem. 2007, H-2 im H-8 nap

Chiral Concave NHC

Can two methyl groups avoid rotation?

NMR Experiments

H-5 nap H-4 ph H-8 nap CDCl 3 No diastereomeric excess!

Increasing the Temperature T = T C T < T C T > T C

VT-NMR Experiments No coalescence!

Synthesis O. Winkelmann, D. Linder, J. Lacour, C. Näther, U. Lüning, Eur. J. Org. Chem. 2007, n = 3,4

Synthesis O. Winkelmann, D. Linder, J. Lacour, C. Näther, U. Lüning, Eur. J. Org. Chem. 2007, n = 3,4

Synthesis n = 3,4 O. Winkelmann, D. Linder, J. Lacour, C. Näther, U. Lüning, Eur. J. Org. Chem. 2007,

Synthesis

Outlook Application of the chiral concave NHC in asymmetric catalysis But first: chiral resolution!

Acknowledgements Lüning group Prof. U. Lüning Travel grant