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

Marcus Korb, Dieter Schaarschmidt, Heinrich Lang

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28 Citations (Scopus)

Abstract

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(eta(5)-C5H3-2-OMe-PPh2)(eta(5)-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.

Original languageEnglish
Pages (from-to)2099-2108
Number of pages10
JournalOrganometallics
Volume33
Issue number8
DOIs
Publication statusPublished - 28 Apr 2014
Externally publishedYes

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