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DOI: 10.1055/s-0031-1290820
Chiral 6-NHC Ligand and Copper Complex: Properties, Application, and Mechanism
Publikationsverlauf
Received: 02. März 2012
Accepted after revision: 09. März 2012
Publikationsdatum:
19. April 2012 (online)
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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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For reactivity of 5-NHC, see:
For insertion reaction, see:
For recent reviews, see:
For recent reviews, see:
For 6-NHC and/or 7-NHC, see:
For Heck reaction using 6-NHC, see:
For hydrogenation reaction using 6- and 7-NHC, see:
For silylation reaction using 6-NHC, see:
For examples, see:
Examples of reactions without using an alcoholic additive, see:
Examples using MeOH or i-PrOH, see:
Example of no effect on reactivity/selectivity, see:
Similar kinetic isotope experiments were done in hydroboration of terminal alkyne by Hoveyda’s group, see: