alpha-Alkylation of ketones was successfully achieved by the reaction of ketones with alcohols catalyzed by iridium complexes in the presence of a small amount of base. For example, 2-octanone was allowed to react with butanol under the influence of [Ir(cod)Cl]2/PPh3/KOH to give 6-dodecanone in good yield. The reaction was found to proceed by using a 1:1 mixture of ketone and alcohol without use of any solvent.

The first Ritter-type reaction of alkylbenzenes with nitriles has been successfully achieved by the use of N-hydroxyphthalimide (NHPI) as a key catalyst. Thus, treatment of ethylbenzene with ammonium hexanitratocerate(IV) (CAN) in the presence of a catalytic amount of NHPI in EtCN under argon produced the corresponding amide in good selectivity.

Clean and selective: Nitrosation and oximation of cycloalkanes was achieved by treating them with tBuONO under Ar in the presence of a catalytic amount of N‐hydroxyphthalimide (see scheme). The novel, clean nitrosation procedure uses halogen‐free, relatively mild reaction conditions and results in good product selectivity (almost no organic byproducts) and high recovery of the catalyst.

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Abstract:The cross-dimerization of an electron-rich terminal alkyne with an electron-deficient internal alkyne was promoted by an iridium complex to produce a 1 : 1 adduct in high regio-and stereoselectivities. This reaction was extended to various combinations of terminal alkynes with internal alkynes such as alkynyl esters and alkynyl aldehydes. The selectivity of the reaction was found to markedly depend on the ligands used. When dppe was used as a ligand, the 1 : 2 cross-cyclotrimerization reaction took place to form substituted benzene derivatives. A plausible reaction path was suggested based on a labeling experiment. This reaction provides a method for the production of complicated enynes which are difficult to be prepared by conventional methods.