A Highly Active Bifunctional Iridium Complex with an Alcohol/Alkoxide-Tethered N-Heterocyclic Carbene for Alkylation of Amines with Alcohols
2012 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 18, no 45, 14510-14519 p.Article, review/survey (Refereed) Published
A series of new iridium(III) complexes containing bidentate N-heterocyclic carbenes (NHC) functionalized with an alcohol or ether group (NHC?OR, R=H, Me) were prepared. The complexes catalyzed the alkylation of anilines with alcohols as latent electrophiles. In particular, biscationic IrIII complexes of the type [Cp*(NHC-OH)Ir(MeCN)]2+2[BF4-] afforded higher-order amine products with very high efficiency; up to >99?% yield using a 1:1 ratio of reactants and 12.5 mol?% of Ir, in short reaction times (216 h) and under base-free conditions. Quantitative yields were also obtained at 50?degrees C, although longer reaction times (4860 h) were needed. A large variety of aromatic amines have been alkylated with primary and secondary alcohols. The reactivity of structurally related iridium(III) complexes was also compared to obtain insights into the mechanism and into the structure of possible catalytic intermediates. The IrIII complexes were stable towards oxygen and moisture, and were characterized by NMR, HRMS, single-crystal X-ray diffraction, and elemental analyses.
Place, publisher, year, edition, pages
2012. Vol. 18, no 45, 14510-14519 p.
amines, carbene ligands, iridium, bifunctional catalyst, synthetic methods
Research subject Organic Chemistry
IdentifiersURN: urn:nbn:se:su:diva-81977DOI: 10.1002/chem.201201845ISI: 000310474800036OAI: oai:DiVA.org:su-81977DiVA: diva2:564864
FunderSwedish Research CouncilKnut and Alice Wallenberg Foundation