Synthesis 2012; 44(10): 1485-1490
DOI: 10.1055/s-0031-1290820
special topic
© Georg Thieme Verlag Stuttgart · New York

Chiral 6-NHC Ligand and Copper Complex: Properties, Application, and Mechanism

Jin Kyoon Park
Department of Chemistry & Biochemistry, Florida State University, Tallahassee, FL 32306-4390, USA, Email: mcquade@chem.fsu.edu
,
D. Tyler McQuade*
Department of Chemistry & Biochemistry, Florida State University, Tallahassee, FL 32306-4390, USA, Email: mcquade@chem.fsu.edu
› Author Affiliations
Further Information

Publication History

Received: 02 March 2012

Accepted after revision: 09 March 2012

Publication Date:
19 April 2012 (eFirst)

Abstract

We demonstrated the synthesis of chiral annulated six-membered-ring N-heterocyclic carbenes (6-NHC) and their adducts with water and alcohol. We also have shown the donating properties of chiral annulated 6-NHCs is between that of typical 5-NHCs and 6-NHCs. We have shown the synthetic conditions for 6-NHC–copper complex formation. Using the chiral 6-NHC–copper complex, we synthesized unsaturated chiral bimetallic allylic boronate reagents with high enantioselectivity. Finally, we propose a catalytic cycle that justifies observed reactivity and provides a new explanation for the role methanol has in the reaction cycle; our cycle is supported by a primary kinetic isotope effect.

 
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