Biocatalytic hydrogen borrowing represents an environmentally friendly and highly efficient synthetic method. This innovative approach involves converting various substrates into high-value-added products, typically via a one-pot, two/three-step sequence encompassing dehydrogenation (intermediate transformation) and hydrogenation processes employing the hydride shuffling between NAD(P) and NAD(P)H. Represented key transformations in hydrogen borrowing include stereoisomer conversion within alcohols, conversion between alcohols and amines, conversion of allylic alcohols to saturated carbonyl counterparts, and α,β-unsaturated aldehydes to saturated carboxylic acids, etc. The direct transformation methodology and environmentally benign characteristics of hydrogen borrowing have contributed to its advancements in fine chemical synthesis or drug developments. Over the past decades, the hydrogen borrowing strategy in biocatalysis has led to the creation of diverse catalytic systems, demonstrating substantial potential for straightforward synthesis as well as asymmetric transformations. This perspective serves as a detailed exposition of the recent advancements in biocatalytic reactions employing the hydrogen borrowing strategy. It provides insights into the potential of this approach for future development, shedding light on its promising prospects in the field of biocatalysis.
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http://dx.doi.org/10.1021/jacsau.4c00026 | DOI Listing |
Angew Chem Int Ed Engl
January 2025
Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford, OX1 3TA, UK.
Compounds containing quaternary stereocentres are a valuable motif in biologically active compounds. Herein we present our strategy to utilise the hydrogen borrowing manifold to access α-quaternary ketones via a tandem acceptorless dehydrogenation-cyclisation cascade. This new application of the methodology results in the formation of five- and six-membered carbocycles with a high degree of diastereoselectivity.
View Article and Find Full Text PDFOrg Biomol Chem
January 2025
Institute for Integrated Programmes and Research in Basic Sciences (IIRBS), Mahatma Gandhi University, Priyadarsini Hills P O, Kottayam, Kerala 686 560, India.
-Alkylation of amines is a vital reaction in the synthesis of numerous bioactive compounds and materials. Among transition metals, palladium has emerged as a particularly effective catalyst for these transformations. The unique advantages of palladium arise from its superior catalytic efficiency, ability to operate under mild conditions, high selectivity and recyclability.
View Article and Find Full Text PDFJ Org Chem
January 2025
Department of Chemistry, Indian Institute of Technology Jodhpur, Karwar, Jodhpur, Rajasthan 342037, India.
An Earth-abundant Mn-PNP pincer complex-catalyzed terpenylation of cyclic and acyclic ketones and secondary alcohol 1-phenylethanol using isoprenoid derivatives prenol, nerol, phytol, solanesol, and E-farnesol as allyl surrogates is reported. The C-C coupling reactions are green and atom-economic, proceeding via dehydrogenation of alcohols following a hydrogen autotransfer methodology aided by metal-ligand cooperation.
View Article and Find Full Text PDFChem Sci
January 2025
Hubei Research Center of Fundamental Science-Chemistry, Engineering Research Center of Organosilicon Compounds & Materials, Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University Wuhan Hubei 430072 China
Developing methodologies for the expedient construction of biologically important δ-valerolactones bearing a privileged azaarene moiety and a sterically congested all-carbon quaternary stereocenter is important and full of challenges. We present herein a novel multicatalytic strategy for the stereodivergent synthesis of highly functionalized chiral δ-valerolactones bearing 1,4-nonadjacent quaternary/tertiary stereocenters by orthogonally merging borrowing hydrogen and Michael addition between α-azaaryl acetates and allylic alcohols followed by lactonization in a one-pot manner. Enabled by Cu/Ru relay catalysis, this cascade protocol offers the advantages of atom/step economy, redox-neutrality, mild reaction conditions, and broad substrate tolerance.
View Article and Find Full Text PDFChem Sci
December 2024
School of Materials Science and Engineering, PCFM Lab, the Key Laboratory of Low-carbon Chemistry & Energy Conservation of Guangdong Province, Sun Yat-sen University Guangzhou 510006 P. R. China
Metal-ligand cooperation (MLC) is an essential strategy in transition metal catalysis. Traditional NH-based and OH-based MLC catalysts, as well as the later developed (de)aromatization strategy, have been widely applied in atom-economic borrowing hydrogen/hydrogen auto-transfer (BH/HA) reactions. However, these conventional MLC approaches are challenging for low-coordination and low-activity coinage metal complexes, arising from the instability during (de)protonation on the coordination atom, the constraint in linear coordination, and possible poisoning due to extra functional sites.
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