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A catalytic β-selective addition of amines to styrenes proceeded in the presence of cationic Ru complexes combined with diphosphine ligands. In the reaction of α-methylstyrene, an enantioselective addition was achieved by using xylylBINAP.

Cyclodehydration of various a-aryloxy ketones proceeded to give various multisubstituted benzofurans by using an Ir(III) catalyst, which was prepared from [Cp*IrCl 2 ] 2 , AgSbF 6 , and Cu(OAc) 2 . The use of the cationic iridium complex with a carboxylate salt realized the efficient transformation at ambient temperature.

Ru-catalyzed S(N)Ar reaction of non-activated fluoroarenes with secondary amines proceeded through eta(6)-arene complexes to give aminated products in up to 79% yield.

Synthesis of naphthalyne-Co2(CO)6 complexes, the first example of the aryne-Co2(CO)6 complex, was achieved via cyclization of acyclic alkyne-Co2(CO)6 complex precursors containing an allylsilane and an aldehyde moiety followed by dehydration. Unique reactivities of the complexes toward oxygen to give carboxylic acid derivatives and toward alkynes to give cyclopentadienone derivatives were also disclosed.

Stereoselective acylation of the E,E-vinylketene silyl N,O-acetal possessing a chiral auxiliary has been achieved by using acid anhydrides and SnCl4. Acid anhydrides having alkyl chains gave the adducts in excellent stereoselectivity. The formal synthesis of khafrefungin has been accomplished by the methodology.

Catalytic S N Ar reaction of fluoroarenes possessing no electron-withdrawing group(s) with cyclic amines was achieved using a readily accessible Ru catalyst, which was prepared from [Ru(benzene)Cl 2 ] 2 , AgOTf, and P(p-FC 6 H 4 ) 3 . The coexistence of molecular sieves MS4A realized high conversion and various substituted aryl amines were obtained in good to high yields.