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

Michael Rubin, Alexander Trofimov, Vladimir Gevorgyan

Research output: Contribution to journalArticle

51 Scopus citations

Abstract

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 13C 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 13C 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 α- and β-vinylstannanes are obtained predominantly for substrates with electron-withdrawing and electron-donating groups, respectively. In the ortho-series, steric factors dominate over electronics and α-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.

Original languageEnglish (US)
Pages (from-to)10243-10249
Number of pages7
JournalJournal of the American Chemical Society
Volume127
Issue number29
DOIs
StatePublished - Jul 27 2005
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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