Metal-catalyzed cross-coupling chemistry with polyhedral boranes

The Metal-Catalyzed Cross-Coupling Reactions of n-Butylketene Dimer

Phosphine catalyzed reduction of CO2 with boranes.

Phosphine is shown to catalyse the reaction of CO2 with 9-BBN to give mixtures of HCO2(B(C8H14)) 3, H2C(OB(C8H14))24 and MeOB(C8H14) 5; at 0.02 mol% of tBu3P 5 is obtained in 98% yield at 60 °C with TON of almost 5500 and a TOF of 170. Under stoichiometric conditions the species (R3PCH2O)(HC(O)O)B(C8H14) (R = tBu 1,4-MeC6H42) were isolated and characterized.

Iron-catalyzed cross-coupling reactions.

Simple iron salts such as FeCl(n), Fe(acac)(n) (n = 2,3) or the salen complex 4 turned out to be highly efficient, cheap, toxicologically benign, and environmentally friendly precatalysts for a host of cross-coupling reactions of alkyl or aryl Grignard reagents, zincates, or organomanganese species with aryl and heteroaryl chlorides, triflates, and even tosylates. An "inorganic Grignard reagent...

Stabilization of Two Radicals with One Metal: A Stepwise Coupling Model for Copper-Catalyzed Radical–Radical Cross-Coupling

Transition metal-catalyzed radical-radical cross-coupling reactions provide innovative methods for C-C and C-heteroatom bond construction. A theoretical study was performed to reveal the mechanism and selectivity of the copper-catalyzed C-N radical-radical cross-coupling reaction. The concerted coupling pathway, in which a C-N bond is formed through the direct nucleophilic addition of a carbon ...

Ruthenium-catalyzed dehydrogenation of ammonia boranes.

The dehydrogenation of ammonia borane (AB) and methylammonia borane (MeAB) is shown to be catalyzed by several Ru-amido complexes. Up to 1 equiv of H2 (1.0 system wt %) is released from AB by as little as 0.03 mol % Ru within 5 min, and up to 2 equiv of H2 (3.0 system wt %) are released from MeAB with 0.5 mol % Ru in under 10 min at room temperature, the first equivalent emerging within 10 s. A...