Boston, G.M.R.; Frank, I.; Butenschön, H.: Anionic Thia-Fries Rearrangement at Ferrocene: A Computational and Experimental Study. In: Helvetica Chimica Acta 104 (2021), Nr. 4, e2100025. DOI: https://doi.org/10.1002/hlca.202100025
Abstract: | |
Ferrocenyl triflate (1) and 1,1′-ferrocenediyl ditriflate (5) undergo single and double anionic thia-Fries rearrangements at low temperatures in high yields with the latter forming exclusively the respective meso product. The detailed mechanisms of the anionic thia-Fries rearrangement of 1, as well as that of the double anionic thia-Fries rearrangement of 5, are examined with the aid of DFT calculations. Functionals, basis set and pseudopotentials applied were selected in accordance with a benchmark using the crystal structure analysis of the prime product 3 of the reaction of 1 before hydrolysis for comparison, which has so far not been reported. The unprecedented meso diastereoselectivity of the double anionic thia-Fries rearrangement of 5 is shown to be a result of a distinctive degree of chelation arising from two diastereomeric transition states. | |
License of this version: | CC BY 4.0 Unported |
Document Type: | Article |
Publishing status: | publishedVersion |
Issue Date: | 2021 |
Appears in Collections: | Naturwissenschaftliche Fakultät |
pos. | country | downloads | ||
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total | perc. | |||
1 | ![]() |
Germany | 7 | 46.67% |
2 | ![]() |
United States | 4 | 26.67% |
3 | ![]() |
Russian Federation | 1 | 6.67% |
4 | ![]() |
Iran, Islamic Republic of | 1 | 6.67% |
5 | ![]() |
Indonesia | 1 | 6.67% |
6 | ![]() |
Egypt | 1 | 6.67% |
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