ISCR—Institut des Sciences Chimiques de Rennes-UMR CNRS 6226, Université de Rennes 1, F-35000 Rennes, France
William Erb
ISCR—Institut des Sciences Chimiques de Rennes-UMR CNRS 6226, Université de Rennes 1, F-35000 Rennes, France
Florence Mongin
ISCR—Institut des Sciences Chimiques de Rennes-UMR CNRS 6226, Université de Rennes 1, F-35000 Rennes, France
Yury S. Halauko
UNESCO Chair of Belarusian State University, 4 Nezavisimosti Av., 220030 Minsk, Belarus
Oleg A. Ivashkevich
Laboratory for Chemistry of Condensed Systems, Research Institute for Physical Chemical Problems of Belarusian State University, 14 Leningradskaya St., 220030 Minsk, Belarus
Vadim E. Matulis
Department of Inorganic Chemistry, Belarusian State University, 4 Nezavisimosti Av., 220030 Minsk, Belarus
Thierry Roisnel
ISCR—Institut des Sciences Chimiques de Rennes-UMR CNRS 6226, Université de Rennes 1, F-35000 Rennes, France
The purpose of the study is to design synthetic methodologies, especially directed deprotometalation using polar organometallic reagents, to access polysubstituted ferrocenesulfoxides. From enantiopure 2-substituted (SiMe3, PPh2) S-tert-butylferrocenesulfoxides, a third substituent was first introduced at the 5 position (SiMe3, I, D, C(OH)Ph2, Me, PPh2, CH2NMe2, F) and removal of the trimethylsilyl group then afforded 2-substituted ferrocenesulfoxides unreachable otherwise. Attempts to apply the “halogen dance” reaction to the ferrocenesulfoxide series led to unexpected results although rationalized in light of calculated pKa values. Further functionalizations were also possible. Thus, new enantiopure, planar chiral di- and trisubstituted ferrocenes have been obtained, in addition to several original 2-substituted, 2,3- and 2,5-disubstituted, 2,3,5-trisubstituted and even 2,3,4,5-tetrasubstituted ferrocenesulfoxides, also enantiopure.
