The development of new reactions allowing an increment of molecular complexity from readily available starting materials, but environmentally friendly and matching the atom-economy is one of the major focuses in modern synthetic organic chemistry. Among the reactions arsenal available for this purpose, metal transition catalyzed reactions have become a powerful tool for constructing complex polycyclic systems under very mild conditions.

Recent progress in computational chemistry has shown that many important chemical and physical properties of the species involved in the metal-transition catalyzed reactions can be predicted from first principles b various computational techniques. This ability is especially important in those cases where experimental results are difficult to obtain.

"Formal" Ru-catalyzed [4+2+2] cycloaddition reaction of 1,6-diynes to 1,3-dienes








Reaction of 1,6-diynos and 1,3-dienes Ru(II)-catalyzed affords 1,3,5-cyclooctatrienes in good yields.

Varela, J. A.; Castedo, L.; Saá, C. Org. Lett. 2003, 5, 2841-2844.

"Formal" Ru-catalyzed [2+2+2] cycloaddition reaction of 1,6-diynes to acyclic alkenes







Reaction of 1,6-diynos and acyclic alkenesRu(II)-catalyzed affords 1,2-cyclohexadienes inmoderated-good yields.

Varela, J. A.; Rubín, S. G.; González-Rodríguez, C.; Castedo, L.; Saá , C. J. Am. Chem. Soc. 2006, 128, 9262-9263.

DFT calculations on "formal" Ru-catalyzed [2+2+2] cycloaddition reactions


The energy potential for the Ru(II)-catalyzed [2+2+2] cycloaddition reaction of two acetylenes and propene has been calculated at the B3LYP level with the double-z LANL2DZ basis set to describe the electrons of the ruthenium atom and for all other atoms the 6-31G* basis set was employed (G in Kcal mol-1 at 298 K and 1 atm.).

Varela, J. A.; Rubín, S. G.; Castedo, L.; Saá, C. J. Org. Chem. 2008, 73, 1330-1332.

Ru-catalyzed cyclizaton reactions of terminal alkynals






Terminal alkynals in the presence of catalytic amounts of Ru(II) species afford cycloalkenes.

Varela, J. A.; González-Rodríguez, C.; Rubín, S. G.; Castedo, L.; Saá , C. J. Am. Chem. Soc. 2006, 128, 9576-9577.