An efficient catalytic system for the alkylation of amines with either alcohols or amines under mild conditions has been developed, using cyclometallated iridium complexes as catalysts. The method has broad substrate scope, allowing for the synthesis of a diverse range of secondary and tertiary amines with good to excellent yields. By controlling the ratio of substrates, both mono- and bis-alkylated amines can be obtained with high selectivity. In particular, methanol can be used as the alkylating reagent, affording N-methylated products selectively. A strong solvent effect is observed for the reaction.

Reaction of perfluoroheptylcopper(i) with (€) -1.2-di-iodoethylene gave (E) -1 H.2H-l-iodopentadecafluoronon-1 -ene (I) which with copper(i) cyanide in dimethylformamide yielded (€) -1 H,2H-1 -cyanopentadecafluoronon-1 -ene (11). Hydrolysis of (11) with sulphuric acid under vigorous conditions afforded (€) -2H.3H-pentadecafluorodec-2-enoic acid (111) whichwas readily hydrogenated to 2H.2H.3H.3H-pentadecafluorodecanoic acid (IV). Reduction of (IV) with lithium aluminium hydride afforded I H.1 H,2H,2H,3H,3H-pentadecafluorodecanol (V). Mild hydrolysis of the nitrile (11) gave (€)-2H.3H-pentadecafluorodec-2-enamide (VI). Reaction of 1.3-diiodohexafluoropropane with copper bronze and an excess of (E) -1.2-di-iodoethylene similarly afforded (1 €,6E) -3,3,4,4,5,5-hexafluoro-l,7-di-iodohepta-l,6-diene (VII) and (1 €,

Reaktion von Perfluorheptyljodid (I) mit Cu und dem Dijodäthylen (II) liefert das Jodnonen (IIIa), das mit CuCN zum Nitril (IIIb) umgesetzt wird.

Conditions. -Aryl amines and aryldiamines as well as primary and secondary acyclic and cyclic amines are N-alkylated with benzylic, primary and secondary alkyl alcohols including methanol. Adjustment of the amount of alcohol used allows for the selective mono or dialkylation, respectively. The new method can also be applied in the cross--coupling of amines. The utility of the method is also demonstrated in the synthesis of pharmacologically relevant Piribedil (XXI) which is employed in the treatment of Parkinson's disease. -(ZOU, Q.; WANG, C.; SMITH, J.; XUE, D.; XIAO*, J.; Chem. -Eur. J. 21 (2015) 27, 9656-9661, http://dx.