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The intermolecular radical functionalization of arenes with aryl and alkyl H‐phosphinate esters, as well as diphenylphosphine oxide and H‐phosphonate diesters, is described. The novel catalytic MnII/excess MnIV system is a convenient and inexpensive solution to directly convert Csp2H into CP bonds. The reaction can be employed to functionalize P‐stereogenic H‐phosphinates since it is stereospecific...
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