Journal
ACS CATALYSIS
Volume 11, Issue 5, Pages 2596-2604Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.0c03437
Keywords
Chemoenzymatic (Chemo-Bio); Electroenzymatic; Heterogenous biocatalysis; Site-separated catalysis; Isotope labeling; Isotopic selectivity; (H2O)-H-2 (D2O); Dihydrogen gas (H-2)
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Funding
- Engineering and Physical Sciences Research Council (EPSRC) IB Catalyst award [EP/N013514/1]
- Linacre College, Oxford
- EPSRC [EP/N013514/1] Funding Source: UKRI
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The study explores a range of catalyst systems for generating deuterium-labeled nicotinamide cofactors and considers their application in driving reductive deuteration reactions. It is shown that the inclusion of an electronically coupled NAD(+)-reducing enzyme offers significant advantages over purely metal systems, yielding exclusively [4S-H-2]-NADH.
Deuterium-labeled nicotinamide cofactors such as [4-H-2]-NADH can be used as mechanistic probes in biological redox processes and offer a route to the synthesis of selectively [H-2] labeled chemicals via biocatalytic reductive deuteration. Atom-efficient routes to the formation and recycling of [4-H-2]-NADH are therefore highly desirable but require careful design in order to alleviate the requirement for [H-2]-labeled reducing agents. In this work, we explore a suite of electrode or hydrogen gas driven catalyst systems for the generation of [4-H-2]-NADH and consider their use for driving reductive deuteration reactions. Catalysts are evaluated for their chemoselectivity, stereoselectivity, and isotopic selectivity, and it is shown that inclusion of an electronically coupled NAD(+)-reducing enzyme delivers considerable advantages over purely metal based systems, yielding exclusively [4S-H-2]-NADH. We further demonstrate the applicability of these types of [4S-H-2]-NADH recycling systems for driving reductive deuteration reactions, regardless of the facioselectivity of the coupled enzyme.
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