Theory and application of photoelectron spectroscopy. 31. Through-conjugation through the sulfone group in 2,5-di-tert-butylthiophene 1,1-dioxide

Mueller, Christian; Schweig, A.; Mock, William L.

doi:10.1021/ja00808a061

Cited by 12 publications

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“…Regio-and siteselectivity for the nitrile oxide -allene cycloadditions calculated using the B3LYP functional and the 6-31G(d,p) basis set.Using DFT to compute the relative TS energy allowed us to naturally introduce the inductive, conjugative and hyperconjugative effects of the sulfonyl group, which caused interpretation difficulties,[24][25][26] and to take entropic effects into consideration. As can be seen, the site-and regioselectivity calculated for the nitrile oxide-sulfonylallene cycloadditions are fully consistent to the experimental findings outlined in theTable 1.…”

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confidence: 99%

Site- and Regioselectivity of Nitrile Oxide–Allene Cycloadditions: DFT-Based Semiquantitative Predictions

Molteni

Ponti

2017

J. Org. Chem.

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Nitrile oxide 1,3-dipolar cycloaddition to arylsulfonyl- and dialkylaminoallenes have been investigated within the framework of the Kohn-Sham density functional theory (DFT) at the B3LYP/6-31G(d,p) level. The hitherto-unexplained experimental behavior of sulfonylallenes was rationalized by transition-state calculations which enabled a semiquantitative treatment of the cycloaddition site- and regioselectivity. The reliability of DFT computations was further established by predicting the complete selectivity of the nitrile oxide cycloaddition to dialkylaminoallenes according to previous experimental findings.

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confidence: 99%