A recent coupling method discovered and developed at DuPont/BMS involves the formation of a carbon-heteroatom bond by the copper acetate promoted oxidative coupling of a boronic acid (stannane, siloxane or iodonium) with an amine, alcohol, or thiol. The advantages of Chan-Lam coupling over Buchwald-Hartwig Pd-catalyzed N/O-arylation reaction are: room temperature and ambient air. Chan-Lam coupling is an extremely versatile and powerful method of synthesis, complementary to Suzuki-Miyaura’s C-C bond cross-coupling. Recent publications.

An extremely useful coupling reaction has recently been developed. Known as Liebeskind-Srogl coupling, this reaction involves the coupling of a boronic acid with a thiol ester to form ketones (J. Am. Chem. Soc. 2000, 122,11260-11261). This reaction is also mechanistically interesting in that the reaction does not use palladium, but uses stoichiometric  copper(I) thiophenecarboxylate (CuTC) as a mediator. The reaction is extremely general and even works with base-sensitive functional groups. 

Kumada coupling is a well-established method for forming carbon-carbon bonds with a Grignard reagent and a aryl, vinyl, or alkyl halide.  The Kumada reaction is less general simply because it is not compatible with any functional groups that react with Grignards.  However, the reaction has the advantage that nickel catalysts can often be used.  Despite it's limitations, the Kumada reaction is a very powerful and inexpensive method of forming simple biaryls. 

Hiyama coupling is the coupling of organosilanes and organohalides.  This method is similar to the Suzuki reaction.  An activating agent such as fluoride is often required.  This reaction has been expanded by the DeShong group to work with siloxanes.

When most cross coupling reactions are performed under a CO atmosphere, the reaction produces a ketone by incorporation of CO. Carbonylative coupling is general nomenclature referring to this type of reaction.  Recent publications

In this reaction an alkyne is coupled to an aromatic halide.  A base and Cu(I) are required.  This reaction is quite general and is an extremely useful method of forming alkynes.  Recent publications

All of the above cross-coupling methods have been used in combinatorial chemistry. In fact, the combinatorial arena as probably the largest growth area. The mild conditions and functional group tolerance of cross-coupling reactions make them perfect  methodologies for forming C-C bonds.  With cross-coupling, difficult and divers molecules can be rapidly and reliably synthesized. Recent publications in combichem.