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A concise manganese(
iii
)-promoted stereoselective β-phosphorylation of acyclic tertiary enamides and diverse H-phosphine oxides was achieved. This reaction proceeds with absolute
E
-selectivity in contrast to
Z
-selectivity obtained in other previous works and affords various
E
-selective β-phosphorylated tertiary enamides in high efficiency. To the best of our knowledge, this is the first case of
E
-selective β-phosphorylation of tertiary enamides through C–H functionalization. In addition, the method features broad substrate scope, good functional group compatibility and efficient scale-up.