Can polarization of triple bond in tolanes be deduced from 13C NMR shifts? Re-evaluation of factors affecting regiochemistry of the palladium-catalyzed hydrostannation of alkynes.
Polarization of the triple bond in a series of differently substituted ortho- and para-tolanes has been studied by NMR and computational methods in order to examine if (13)C NMR data can be effectively used for the assessment of electronic polarization of a triple bond in diarylacetylenes. DFT calculations of both natural charges and NMR properties revealed that chemical shifts concur with effective charges on sp-carbon atoms in para-tolanes, whereas in ortho-analogues magnetic anisotropy complicates the analysis making (13)C NMR data inapplicable for ascribing triple bond polarization. The obtained information was used to reevaluate factors affecting the regiochemistry of the Pd-catalyzed hydrostannation of the triple bond in tolanes. Computational study on the polarization of triple bonds taken together with the experimental data on hydrostannation of various mono- and disubstituted tolanes bearing para- and ortho-substituents demonstrated that the regioselectivity of hydrostannation is governed by a combination of electronic and steric factors. In para-tolanes, the electronic effect prevails and alpha- and beta-vinylstannanes are obtained predominantly for substrates with electron-withdrawing and electron-donating groups, respectively. In the ortho-series, steric factors dominate over electronics and alpha-isomers are produced with high selectivity regardless of the substituents' nature. However, it was found that in disubstituted "push-pull" tolanes steric control of an ortho-group can be overruled by the very strong electronic effect of an electron-withdrawing substituent in para-position.
Rubin
Michael
M
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, Illinois 60607-7061, USA.
Trofimov
Alexander
A
Gevorgyan
Vladimir
V