Abstract
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.
Highlights
IntroductionThe sulfoxide group (of general formula RSOR’) has attracted the interest of chemists because of its good accessibility and specific reactivity [1–10]
During the last decades, the sulfoxide group has attracted the interest of chemists because of its good accessibility and specific reactivity [1–10]
During the synthesis of enantiopure ferrocene-1,2-disulfoxides that we recently reported, we showed that these reduction/oxidation steps could be avoided by adapting the reaction conditions [46]
Summary
The sulfoxide group (of general formula RSOR’) has attracted the interest of chemists because of its good accessibility and specific reactivity [1–10]. An additional feature of sulfoxides lies in their chirality (when R 6= R’) which can be used to control the stereochemical outcome of many transformations [11]. Since the discovery of their parent compound in 1952 [20,21], ferrocenes have established themselves as one of the most important families of organometallics These three-dimensional compounds in which the iron is surrounded by two cyclopentadienyl rings are often stable to air, water, heat and light, and exhibit a reversible redox behavior. They can bring specific physical and chemical properties to the molecules in which they are included [22]. They have found many applications in fields such as catalysis [23–25], medicinal chemistry [26–28], and material science [29,30]
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