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An efficient N‐heterocyclic carbene‐catalyzed oxidative esterification reaction of aldehydes with alkyl halides or alkyl 4‐methylbenzenesulfonate is reported. It was worth noting that (1) the configuration of alkyl halides or alkyl 4‐methylbenzenesulfonates was inverted completely, and (2) the presence of oxygen was crucial for this transformation. The reaction proceeded smoothly under mild conditions...