| Summary: | 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 (SiMe<sub>3</sub>, PPh<sub>2</sub>) <i>S</i>-<i>tert</i>-butylferrocenesulfoxides, a third substituent was first introduced at the 5 position (SiMe<sub>3</sub>, I, D, C(OH)Ph<sub>2</sub>, Me, PPh<sub>2</sub>, CH<sub>2</sub>NMe<sub>2</sub>, 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 p<i>K</i><sub>a</sub> 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.
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