We present a highly deuterium atom economical approach for the synthesis of deuterated alcohols via the single electron transfer (SET) reductive deuteration of acyl chlorides. Cost-effective sodium dispersion and EtOD- were used as the single electron donor and deuterium donor, respectively. Our approach achieved up to 49% deuterium atom economy, which represents the highest deuterium atom economy yet achieved in SET reductive deuteration reactions. With all 20 tested substrates, excellent regioselectivity and >92% deuterium incorporations were obtained. Furthermore, we demonstrated the potential of this methodology by synthesizing four deuterated analogues of pesticides.
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