Preparation of planar chiral ferrocenes containing a fluorous alcohol function

Ferrocene reacts with hexafluoroacetone trihydrate in refluxing octane to afford >80% yields of [CpFe(η5-C5H4C(CF3)2OH)] (X-ray), carrying out the reactions at 180 °C gives an additional 5% yield of [Fe(η5-C5H4C(CF3)2OH)2] (X-ray).The mono alcohol is lithiated with ButOK/BunLi/TMEDA affording partial conversion to mixtures of [CpFe(1,2-η5-C5H3C(CF3)2OH)(X)] and [Fe(η5-C5H4X)(1,2-η5-C5H3C(CF3)2OH)(X)] (X = SMe, CPh2OH) upon reaction with Me2S2 or Odouble bond; length as m-dashCPh2.For X = CPh2OH both structures are crystallographically characterised.Enantiopure [CpFe(1,2-η5-C5H3C(CF3)2OH)(SMe)] can be prepared from (R)-[CpFe(η5-C5H4S(O)C6H4Me)] via [CpFe(1,2-η5-C5H3S(O)C6H4Me)(C(CF3)2OH)] (X-ray) or [CpFe(1,2-η5-C5H3S(O)C6H4Me)(SMe)].Related procedures allow the preparation of [CpFe(1,2-η5-C5H3CPh2OH)(Y)] (Y = SMe, CHO (X-ray), C(CF3)2OH) and[CpFe(1,2-η5-C5H3C(CF3)2OH)(CHO)].