Iridium­(I) complexes having an imidazol-2-ylidene ligand with benzylic wingtips efficiently catalyzed the β-alkylation of secondary alcohols with primary alcohols and acceptorless dehydrogenative cyclization of 2-aminobenzyl alcohol with ketones through a borrowing hydrogen pathway. The β-alkylated alcohols, including cholesterol derivatives, and substituted quinolines were obtained in good yields by using a minute amount of the catalyst with a catalytic amount of NaOH or KOH under the air atmosphere, liberating water (and H2 in the case of quinoline synthesis) as the sole byproduct. Notably, this system demonstrated turnover numbers of 940 000 (for β-alkylation of secondary alcohols with primary alcohols by using down to 0.0001 mol % = 1 ppm of the catalyst) and 9200 (acceptorless dehydrogenative cyclization of 2-aminobenzyl alcohol with ketones).

α-Alkylation of arylacetonitriles with primary alcohols was achieved by using backbone-modified NHC–IrI complexes as catalysts with turnover numbers of up to 960.

Key indicatorsSingle-crystal X-ray study T = 293 K Mean '(C±C) = 0.003 A Ê R factor = 0.037 wR factor = 0.115 Data-to-parameter ratio = 15.6For details of how these key indicators were automatically derived from the article, see

The nickel(II)-salen or nickel(II)-salphen catalyzed α-alkylation of ketones and nitriles with primary alcohols is reported. Various α-alkylated ketones and nitriles were obtained in high yields through a borrowing hydrogen strategy...

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related problem, the field of Molecular Magnetism is currently shifting towards more complicated systems. One direction has been opened by the observation of slow relaxation of the magnetization in 1D systems (called Single Chain Magnets or SCMs). Synthetic efforts are devoted to the development of new systems SCMs that can help us understanding the physical background that lies beneath this phenomenon. In this contest several groups have development new tools allowing for the engineering of both magnetic and structural properties. Here we discuss some opportunities offered by the Metal Nitronilnitroxyde strategy. In particular the experimental and theoretical work developed on finite-size effects revealed itself a key point. We describe the rational strategy that allowed creating the first rare-earth based SCMs. We show that we can freely substitute the metallic centres without structural alterations, thus tuning of the magnetic properties. This affords a useful information on the key parameters that rule SCMs.

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