Anionic Phospho-Fries Rearrangement at Ferrocene: One-Pot Approach to P,O-Substituted Ferrocenes

For the first time the anionic phospho-Fries rearrangement has been successfully applied in ferrocene chemistry, giving access to 1,2-P,O-substituted ferrocenes. The 1,3 (O → C)-migration occurs at ferrocenyl phosphates, thiophosphates, phosphite–borane adducts, and phosphinates by treatment with a...

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Bibliographic Details
Published in:Organometallics 2014-04, Vol.33 (8), p.2099-2108
Main Authors: Korb, Marcus, Schaarschmidt, Dieter, Lang, Heinrich
Format: Article
Language:English
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Summary:For the first time the anionic phospho-Fries rearrangement has been successfully applied in ferrocene chemistry, giving access to 1,2-P,O-substituted ferrocenes. The 1,3 (O → C)-migration occurs at ferrocenyl phosphates, thiophosphates, phosphite–borane adducts, and phosphinates by treatment with a base such as lithium diisopropylamide at low temperature, whereas the highest yields were obtained starting from diethylferrocenyl phosphate. Complete reduction of the phosphonate to a primary phosphine and subsequent Stelzer P,C cross coupling allowed the synthesis of Fe(η5-C5H3-2-OMe-PPh2)(η5-C5H5) (1). The qualification of 1 as a supporting ligand in palladium-catalyzed Suzuki–Miyaura C,C couplings has been proven by the synthesis of sterically congested tri-ortho-substituted biaryls under mild reaction conditions in good to excellent yields.
ISSN:0276-7333
1520-6041
DOI:10.1021/om5002827