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Anionic Thia‐ Fries Rearrangement at Ferrocene: A Computational and Experimental Study
Author(s) -
Boston Geanne M. R.,
Frank Irmgard,
Butenschön Holger
Publication year - 2021
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.202100025
Subject(s) - chemistry , fries rearrangement , trifluoromethanesulfonate , diastereomer , rearrangement reaction , medicinal chemistry , stereochemistry , computational chemistry , catalysis , organic chemistry
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.