Nobuaki Kambe

Cross-coupling reactions have become indispensable tools for creating carbon-carbon (or heteroatom) bonds in organic synthesis. Like in other important transition metal catalyzed reactions, such as metathesis, addition, and polymerization, unsaturated compounds are usually employed as substrates for cross-coupling reactions. However during the past decade, a great deal of effort has been devoted to the use of alkyl halides as saturated compounds in cross-coupling reactions, which has resulted in

Gelungene Verbindung: Die Cu-katalysierte Kreuzkupplung zwischen primären Alkylhalogeniden und primären, sekundären und tertiären Alkyl- sowie Phenyl-Grignard-Reagentien verläuft in THF unter Rückfluss in Gegenwart von 1-Phenylpropin effizient (siehe Schema). Die Reaktion gelingt auch mit Alkylmesylaten (OMs) und -tosylaten (OTs). Die Alkyl-X-Reaktivitäten gegenüber dem Grignard-Reagens nehmen in der Reihenfolge X=Cl<F<OMs<OTs<Br zu. Supporting information for this article is available on the WW

Compounds of the type Rli , with R PhC°C, PhCH 2 Ph, CH 2  CHCH 2 , alkyl, Me 3 SiCH 2 , PhCH 2 OCH 2 , etc., can be generated in an indirect way by the route shown below. In a one‐pot procedure, the tellurides are formed directly from alkyl halides and tellurolates RTeLi. The procedure particularly valuable when conventional lithium‐halogen exchange is not possible. equation image

A simple method for the conversion of (sp(3))C-F bonds of alkyl fluorides to (sp(3))C-X (X = Cl, C, H, O, S, Se, Te, N) bonds has been achieved by the use of a hexane solution of organoaluminum reagents having Al-X bonds.

The direct sulfenylation and sulfonylation of (sp(2))C-H bonds of benzamide derivatives were achieved using a Ni catalyst with the aid of an 8-aminoquinoline moiety as a bidentate directing group. These protocols represent a convenient route for the formation of valuable diaryl sulfides and sulfones in moderate to excellent yields.

A facile method for the conversion of C-F bonds of benzotrifluorides to C-C bonds has been developed using aluminium reagents in the absence of catalysts.

A new method for the regioselective three-component cross-coupling of alkyl halides, alkynes, or enynes with organomagnesium or organozinc reagents in the presence of a nickel catalyst and a dppb ligand has been developed.

The cross-coupling of Grignard reagents with alkyl bromides and tosylates has been achieved by the use of eta(3)-allylnickel and eta(3)-allylpalladium complexes as catalysts.