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A step‐economical and operationally simple nickel‐catalyzed cross‐electrophile coupling of aryl phosphates with aryl bromides through C−O bond cleavage, which precluded the employment of relatively moisture‐labile and unreadily available organometallics, was developed. The reaction proceeded smoothly in the presence of magnesium turnings and lithium chloride in THF to afford the corresponding biaryls...
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