Rhodium- and palladium-catalyzed 1,5-substitution reactions of 2-en-4-yne acetates and carbonates with organoboronic acids.

Two methods involving the rhodium-catalyzed reaction of 2-en-4-yne acetates and the palladium-catalyzed reaction of 2-en-4-yne carbonates with organoboronic acids were investigated; both afforded exclusively the (E)-configured vinylallenes. The coordinative interaction of the rhodium with the acetate group promoted the δ-elimination of Rh(I)-OAc from the alkenylrhodium intermediate II in both syn and anti modes, with the syn-elimination being the major path. DFT calculations revealed that a conformer of this intermediate (II), which can lead to the (E)-configured vinylallene product via the syn-elimination mode, is energetically the most favorable conformer. The rhodium-catalyzed procedure is not applicable to reactions involving (E)-configured enyne acetates, because the geometry of the alkenylrhodium intermediate that is derived from the corresponding (E)-enyne acetate would not allow such coordinative interaction to occur. The palladium-catalyzed method, which proceeds through formation of the σ-vinylallenylpalladium intermediate, B, is suitable for both the (E)- and (Z)-configured enyne carbonates and appears to have a wider scope for both organoboronic acids and enyne substrates. The palladium-catalyzed reaction of an enantiomerically enriched enyne carbonate proceeded with racemization.

Rhodium catalysed chemo- and stereoselective arylative and alkenylative cyclisation reactions of unsymmetric diynes containing a terminal alkyne moiety with organoboronic acids.

Unsymmetric diynes possessing a terminal alkyne moiety reacted with organoboronic acids both chemo- and stereoselectively to afford arylated or alkenylated exocyclic dienes by catalysis from the [Rh(cod)OCH(3)](2) complex. The use of a polar protic solvent, e.g. CH(3)OH is required for the success of the process under mild conditions.