Asymmetric electrocatalysis is poised to provide a unique avenue for access to enantioenriched molecules that are difficult to obtain through more conventional approaches, but the development of efficient electrocatalysts capable of highly enantioselective transformations remains elusive. Towards this enviable end, bifunctional electrocatalyst capable of both redox mediation and delivery of high stereocontrol is needed. Here we disclose a novel TEMPO-BOX-ligated copper electrocatalyst that enables oxidative kinetic resolution of racemic 1,4-diols, affording diverse chiral 1,4-diols and γ-lactones with good or excellent chemo-, regio, and enantioselectivity. We also show that this cooperative Cu/TEMPO-BOX catalytic strategy is applicable to the electro-oxidative kinetic resolution of 1,2- and 1,3-amino alcohols. This work demonstrates the potential of bifunctional electrocatalysis for asymmetric synthetic methods and we anticipate that it will spur the development of new hybrid electrocatalysts to realize novel asymmetric electrocatalytic methods.
Summary While formaldehyde is an emerging C1 resource for the synthesis of high value-added chemicals due to its high and versatile reactivity, selective activation and controllable transformation of formaldehyde still remains a great challenge. In particular, coupling of formaldehyde with small aldehydes such as 3-hydroxypropanal offers excellent opportunity for constructing valuable molecules but has not been realized. A benzaldehyde lyase from Herbiconiux sp. SALV-R1 was engineered through directed evolution to achieve the coupling of 3-hydroxypropanal and formaldehyde. A carbonyl reductase and a transaminase were identified to catalyze reduction or transamination of 1,4-dihydroxybutan-2-one, a highly functionalized small ketone. The newly attained enzymatic hydroxymethylation and asymmetric reduction or transamination were then combined with the chemocatalytic hydration of acrolein in a one-pot process to synthesize optically pure 1,2,4-butanetriol and 2-aminobutane-1,4-diol from acrolein and formaldehyde. These results exemplify a new way for sustainable synthesis of high value-added chemicals from C1 molecules and simple starting materials.
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