TY - JOUR
T1 - Anionic Thia-Fries Rearrangement at Ferrocene
T2 - A Computational and Experimental Study
AU - Boston, Geanne M.R.
AU - Frank, Irmgard
AU - Butenschön, Holger
N1 - Funding Information:
The authors thank Dr. Michael Wiebcke, Institut für Anorganische Chemie, Leibniz Universität Hannover, for the X‐Ray crystallographic measurement. We appreciate a donation of ferrocene by . This work was supported by the computer cluster funded by the Leibniz Universität Hannover, the Lower Saxony Ministry of Science and Culture (MWK) and the (DFG). Open access funding enabled and organized by Projekt DEAL. Innospec Deutschland GmbH Deutsche Forschungsgemeinschaft
PY - 2021/4/14
Y1 - 2021/4/14
N2 - 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.
AB - 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.
KW - anionic thia-Fries rearrangement
KW - crystal structure analysis
KW - density functional calculations
KW - ferrocenyl triflates
KW - reaction mechanisms
UR - https://www.scopus.com/pages/publications/85103090861
U2 - 10.1002/hlca.202100025
DO - 10.1002/hlca.202100025
M3 - Article
AN - SCOPUS:85103090861
SN - 1522-2675
VL - 104
JO - Helvetica Chimica Acta
JF - Helvetica Chimica Acta
IS - 4
M1 - e2100025
ER -