A concise manganese(III)-promoted stereoselective β-phosphorylation of acyclic tertiary enamides and diverse H-phosphine oxides was achieved. This reaction proceeds with absolute -selectivity in contrast to -selectivity obtained in other previous works and affords various -selective β-phosphorylated tertiary enamides in high efficiency. To the best of our knowledge, this is the first case of -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.
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