Translating the power of transition metal catalysis to the native habitats of enzymes can significantly expand the possibilities of interrogating or manipulating natural biological systems, including living cells and organisms. This is especially relevant for organometallic reactions that have shown great potential in the field of organic synthesis, like the metal-catalyzed transfer of carbenes. While, at first sight, performing metal carbene chemistry in aqueous solvents, and especially in biologically relevant mixtures, does not seem obvious, in recent years there has been a growing number of reports demonstrating the feasibility of the task. Either using small molecule metal catalysts or artificial metalloenzymes, a number of carbene transfer reactions that tolerate aqueous and biorelevant media are being developed. This review intends to summarize the most relevant contributions, and establish the state of the art in this emerging research field.
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http://dx.doi.org/10.1039/d2sc00721e | DOI Listing |
Angew Chem Int Ed Engl
January 2025
University of York, Chemistry, Heslington, YO105DD, York, UNITED KINGDOM OF GREAT BRITAIN AND NORTHERN IRELAND.
A tandem catalytic ensemble of solid-state molecular organometallic (SMOM) crystalline pre-catalysts are deployed under batch or flow conditions for the ethene to propene process (ETP). These catalysts operate at ambient temperature and low pressure, via sequential ethene dimerization, butenes isomerization and cross-metathesis. Under flow conditions the on-stream ethene conversion (55%), initial propene selectivity (92%), stability (71% selectivity after 7 hrs) and low temperature/pressures are competitive with the best-in-class heterogenous systems, marking a new, in crystallo, approach to ETP.
View Article and Find Full Text PDFNat Commun
January 2025
State Key Laboratory of Organometallic Chemistry, Shanghai of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai, PR China.
Motivated by the inherent benefits of synergistically combining electrochemical methodologies with nickel catalysis, we present here a Ni-catalyzed enantioselective electroreductive cross-coupling of benzyl chlorides with aryl halides, yielding chiral 1,1-diaryl compounds with good to excellent enantioselectivity. This catalytic reaction can not only be applied to aryl chlorides/bromides, which are challenging to access by other means, but also to benzyl chlorides containing silicon groups. Additionally, the absence of a sacrificial anode lays a foundation for scalability.
View Article and Find Full Text PDFACS Cent Sci
January 2025
Department of Chemistry, Zhejiang University, Hangzhou 310058, China.
Recently, nickel catalysts have garnered considerable attention for their efficacy and versatility in asymmetric catalysis, attributed to their distinctive properties. However, the use of cost-effective and sustainable divalent nickel catalysts in C-H activation/asymmetric alkene insertion poses significant challenges due to the intricate control of stereochemistry in the transformation of the tetracoordinate C-Ni(II) intermediate. Herein, we report a Ni(II)-catalyzed enantioselective C-H/N-H annulation with oxabicyclic alkenes.
View Article and Find Full Text PDFNat Chem
January 2025
TUM School of Natural Sciences, Department of Chemistry, Chair of Inorganic and Metal-Organic Chemistry and Catalysis Research Center, Technical University of Munich, Garching, Germany.
The exploration of ligated metal clusters' chemical space is challenging, partly owing to an insufficiently targeted access to reactive clusters. Now, dynamic mixtures of clusters, defined as living libraries, are obtained through organometallic precursor chemistry. The libraries are populated with interrelated clusters, including transient and highly reactive ones, as well as more accessible but less reactive species.
View Article and Find Full Text PDFAcc Chem Res
January 2025
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
ConspectusIn recent years, our research group has dedicated significant effort to the field of asymmetric organometallic electrochemical synthesis (AOES), which integrates electrochemistry with asymmetric transition metal catalysis. On one hand, we have rationalized that organometallic compounds can serve as molecular electrocatalysts (mediators) to reduce overpotentials and enhance both the reactivity and selectivity of reactions. On the other hand, the conditions for asymmetric transition metal catalysis can be substantially improved through electrochemistry, enabling precise modulation of the transition metal's oxidation state by controlling electrochemical potentials and regulating the electron transfer rate via current adjustments.
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