Coinage Metal Complexes of Chiral N‐Heterocyclic Carbene Ligands: Syntheses and Applications in Asymmetric Catalysis

• Published in: Advanced synthesis & catalysis Vol. 362; no. 5; pp. 970 - 997
• Main Authors: Budagumpi, Srinivasa, Keri, Rangappa S., Achar, Gautam, Brinda, K. N.
• Format: Journal Article
• Language: English
• Published: Heidelberg Wiley Subscription Services, Inc 04.03.2020
• Subjects: Alkenes; asymmetric cyclization; Asymmetry; Carbenes; Catalysis; Catalytic activity; chiral N-heterocyclic carbenes; coinage metals; conjugate addition; Coordination compounds; Hydrosilylation; Ketones; Ligands; Organic chemistry; Organometallic compounds
• ISSN: 1615-4150; 1615-4169
• DOI: 10.1002/adsc.201900859

Chiral N‐heterocyclic carbenes (NHCs) have become ligands of choice due to their remarkable catalytic activity in organic transformation reactions. Combining the chiral NHC ligand family and coinage metals became a productive area of research. The organometallic chemistry of coinage metals with the chiral N‐heterocyclic carbene (NHC) ligands is reviewed, with a special emphasis on the synthesis, characterization and possible applications obtained. Significant sections are devoted to the various recently developed coinage metal‐chiral NHC complexes and a detailed comparison of their activities which aims to rationalize the structure–activity relationships. Various methods of preparations of coinage metal‐chiral NHC complexes along with some typical examples of reactivity and mechanisms are covered. Cu‐chiral NHC complexes involved in conjugated additions, allylic substitutions, boration of alkenes, hydrosilylation of ketones and formation of alkenes are covered, along with some remarkable examples and reactivity of Ag‐chiral NHC complexes. Finally, applications of Au‐chiral NHC complexes in the asymmetric cyclization of ester‐functionalized 1,6‐enynes, 1,6‐enyneamines and substituted propargyloxymethanes are also reviewed.