Reduction and alkylation of (η6-arene)tricarbonylmanganese complexes using alkyl-substituted coenzyme NADH models

• tert-Butyl group transfer was observed between t-BuBNAH and (η6-arene)Mn(CO)3+ complexes without a radical initiator.
• Hantzsch ester with isopropyl substituent at the C4 position undergo isopropyl transfer to (η6-benzene)Mn(CO)3+ complex.
• The substituents on the aromatic ring significantly influence the reactivity and chemoselectivity.
• The present alkyl group transfer reactions exhibit different reactivity pattern from organomercurials and indium system.

The direct tert-butyl group transfer was observed between t-BuBNAH and (η6-arene)Mn(CO)3+ complexes in reflux acetonitrile without a radical initiator, and the corresponding tert-butyl radical addition products were achieved. The substituents on the aromatic ring significantly influence the reactivity and chemoselectivity. The electron-withdrawing group helps to promote the reactions. The radical inhibition experiment indicated that the reaction is probably a radical chain process initiated by single electron transfer.

The direct tert-butyl group transfer was observed between t-BuBNAH and (η6-arene)Mn(CO)3+ complexes in reflux acetonitrile without a radical initiator, and the corresponding tert-butyl radical addition products were achieved.Figure optionsDownload as PowerPoint slide