Catalytic non-conventional trans-hydroboration: a theoretical and experimental perspective.
We have studied the non-conventional trans-hydroboration reaction of alkynes both experimentally and theoretically. A catalytic system based on the in situ mixture of [{Rh(cod)Cl}(2)]/PCy(3) (cod=1,5-cyclooctadiene, Cy=cyclohexyl) has been able to activate pinacolborane and catecholborane and transfer boryl and hydride groups onto the same unhindered carbon atom of the terminal alkynes. The presence of a base (Et(3)N) favored the non-conventional trans-hydroboration over the traditional cis-hydroboration. Varying the substrate had a significant influence on the reaction, with up to 99% conversion and 94% regioselectivity observed for para-methyl-phenylacetylene. Both DFT and quantum mechanical/molecular mechanical ONIOM calculations were carried out on the [RhCl(PR(3))(2)] system. To explain the selectivity towards the (Z)-alkenylboronate we explored several alternative mechanisms to the traditional cis-hydroboration, using propyne as a model alkyne. The proposed mechanism can be divided into four stages: 1) isomerization of the alkyne into the vinylidene, 2) oxidative addition of the borane reagent, 3) vinylidene insertion into the Rh-H bond, and finally 4) reductive elimination of the C-B bond to yield the 1-alkenylboronate. Calculations indicated that the vinylidene insertion is the selectivity-determining step. This result was consistent with the observed Z selectivity when the sterically demanding phosphine groups, such as PCy(3) and PiPr(3), were introduced. Finally, we theoretically analyzed the effect of the substrate on the selectivity; we identified several factors that contribute to the preference for aryl alkynes over aliphatic alkynes for the Z isomer. The intrinsic electronic properties of aryl substituents favored the Z-pathway over the E-pathway, and the aryl groups containing electron donating substituents favored the occurrence of the vinylidene reaction channel.
Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, C/Marcel.lí Domingo s/n, 43007, Tarragona, Spain.
Jessica
J
Cid
Jorge J
JJ
Carbó
Elena
E
Fernández