TY - JOUR AU - Park, Jin Kyoon; McQuade, D. Tyler TI - Chiral 6-NHC Ligand and Copper Complex: Properties, Application, and Mechanism SN - 0039-7881 SN - 1437-210X PY - 2012 JO - Synthesis JF - Synthesis LA - EN VL - 44 IS - 10 SP - 1485 EP - 1490 ET - 2012/04/19 DA - 2012/05/07 KW - bimetallic reagents KW - copper KW - boron KW - carbene complex KW - enantioselective substitution AB - 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. PB - © Georg Thieme Verlag DO - 10.1055/s-0031-1290820 UR - http://www.thieme-connect.de/products/ejournals/abstract/10.1055/s-0031-1290820 ER -