Nature Chemistry, Published online: 28 February 2024; doi:10.1038/s41557-024-01463-7
Developing a generalizable method for blocking and rescuing tryptophan (Trp) interactions would enable the gain-of-function manipulation of various Trp-containing proteins but has so far been challenging. Now a genetically encoded N1-vinyl-caged Trp capable of rapid and bioorthogonal decaging enables site-specific activation of Trp on a protein of interest within living cells.Shared posts
Enantioselective synthesis of multifunctional alkylboronates via N-heterocyclic carbene–nickel-catalysed carboboration of alkenes
Nature Synthesis, Published online: 07 March 2024; doi:10.1038/s44160-024-00492-x
Multicomponent catalytic reactions that generate enantioenriched boronic esters are underdeveloped. Now an N-heterocyclic carbene–nickel catalyst promotes enantioselective alkene 1,2-carboboration to access multifunctional alkylboronates, bearing a tertiary or quaternary β-stereocentre.[ASAP] Asymmetric Synthesis of α-Chloroamides via Photoenzymatic Hydroalkylation of Olefins
BracaChemoselectivity improved by evolution 🧬🙌🏼
Catalytic Chain Transfer in Crosslinking Photopolymerizations
Synlett
DOI: 10.1055/a-2256-2980
Presented here is a detailed account of the development and implementation of macrocyclic cobaloxime complexes as sulfur-free, catalytic chain transfer agents (CTAs) in crosslinking photopolymerizations. Although much of this review is dedicated to understanding the fundamentals of catalytic chain transfer (CCT) in photopolymerizations, its impact on network topology and resultant mechanical properties, future goals of applying this technology to multimaterial 3D printing are also discussed. It is our long-term ambition for catalytic, sulfur-free CTAs to supplant existing consumptive, sulfur-based agents to provide new, unexplored, and not currently possible to fabricate photopolymeric materials with a specific eye towards application in dentistry, additive manufacturing, and responsive materials.1 Introduction2 History of Catalytic Chain Transfer (CCT)3 Understanding Catalyst Purity and Chain Transfer Activity4 Evidencing CCT in a Crosslinking Photopolymerization5 Comparing Cobalt(II)-Catalysts to Other Relevant CTAs6 Performance of Cobalt(II)-Catalysts in Commercial Resins7 Limitations of Approach and Looking Forward
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Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
Article in Thieme eJournals:
Table of contents | Abstract | Full text
Directed Evolution of Protoglobin Optimizes the Enzyme Electric Field
A de novo metalloenzyme for cerium photoredox catalysis
A non-canonical nucleophile unlocks a new mechanistic pathway in a designed enzyme
Nature Communications, Published online: 04 March 2024; doi:10.1038/s41467-024-46123-z
The authors previously showed that a histidine nucleophile and a flexible arginine can work in synergy to accelerate the Morita Baylis-Hillman (MBH) reaction. Here, they report another efficient MBHase that employs a non-canonical Nδ-methylhistidine nucleophile paired with a catalytic glutamate, providing an alternative mechanistic solution for MBH catalysis.[ASAP] Gold(I) Complex with a Photoactive Ligand Behaves as a Two-in-One Dual Metallaphotoredox Cross-Coupling Catalyst
Silver-catalyzed direct conversion of epoxides into cyclopropanes using N-triftosylhydrazones
Nature Communications, Published online: 02 March 2024; doi:10.1038/s41467-024-46188-w
Epoxides are prominent small-ring O-heterocycles found in a variety of bioactive natural products and pharmaceuticals. Here, the authors report a silver carbene strategy to achieve O-to-C atom exchange of epoxides in a single step, affording diverse fluoroalkylcyclopropanes.The impact of UV light on synthetic photochemistry and photocatalysis
Nature Chemistry, Published online: 01 March 2024; doi:10.1038/s41557-024-01472-6
Although generally perceived as an old-fashioned and unselective tool to build molecules, the photochemistry community is now re-discovering the power of UV light and is using key mechanistic information to develop new catalytic processes driven by visible light. This Perspective discusses the progress and impact of UV light in organic synthesis.Effective engineering of a ketoreductase for the biocatalytic synthesis of an ipatasertib precursor
Communications Chemistry, Published online: 28 February 2024; doi:10.1038/s42004-024-01130-5
Ipatasertib is a potent Akt (protein kinase B) inhibitor synthesized via a chemoenzymatic process. Here, the authors use mutational scanning and algorithm-aided enzyme engineering to optimize a ketoreductase from Sporidiobolus salmonicolor and generate a 10-amino acid substituted variant exhibiting a 64-fold higher kcat and improved yield for the relevant alcohol intermediate, with ≥ 98% conversion and a diastereomeric excess of 99.7% (R,R-trans) from 100 g L−1 ketone after 30 h.Manganese(I)-Catalyzed C–H Allylation of Tryptophans and Their Oligopeptides On Water
Synlett
DOI: 10.1055/a-2268-4678
The manganese(I)-catalyzed allylation of the amino acid tryptophan is realized under exceedingly mild conditions using water as a sustainable and non-hazardous reaction medium, instead of classical organic solvents, with great potential for green and sustainable chemistry. Synthetically useful α,β-unsaturated esters can be accessed by reaction with Morita–Baylis–Hillman (MBH) adducts following a fast C–H activation approach. The robustness of this procedure is reflected by kinetic analysis at different reaction temperatures and reduced catalyst loadings are employed.
[...]
Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
Article in Thieme eJournals:
Table of contents | Abstract | Full text
[ASAP] Ni-Catalyzed Photochemial Sulfamidation of Aryl Chlorides with Soluble Organic Amine as Base
Biocatalysis: landmark discoveries and applications in chemical synthesis
DOI: 10.1039/D3CS00689A, Tutorial Review
This tutorial review will give readers an insight into the landmark discoveries and milestones that have helped shape and grow the field of biocatalysis since the discovery of the first enzyme.
To cite this article before page numbers are assigned, use the DOI form of citation above.
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Boosting N-Heterocyclic Carbene Radical Organocatalysis with Nickel Chemistry: A Rational Mechanistic Study-based Approach.
Light-induced Pd catalyst enables C(sp2)–C(sp2) cross-electrophile coupling bypassing the demand for transmetalation
Nature Catalysis, Published online: 20 February 2024; doi:10.1038/s41929-024-01109-4
The direct cross-electrophile coupling of (hetero)aryl halides and pseudohalides is challenging. Now this reaction is facilitated by a visible light-induced palladium catalytic system that differentiates the reactants on the basis of the bond dissociation enthalpy affording unsymmetrical (hetero)biaryls.[ASAP] Orthogonal Translation for Site-Specific Installation of Post-translational Modifications
Artificial Metalloenzyme Catalyzed Enantioselective Carboamination of Alkenes
[ASAP] Near-Infrared Photoredox Catalyzed Fluoroalkylation Strategy for Protein Labeling in Complex Tissue Environments
[ASAP] 1,3-Butadiene Dicarbofunctionalization Enabled by the Dual Role of Diaryl Ketone in Photo-HAT/Chromium Catalysis
Iron-catalyzed fluoroalkylative alkylsulfonylation of alkenes via radical-anion relay
Nature Communications, Published online: 17 February 2024; doi:10.1038/s41467-024-45867-y
Stoichiometric amounts of metal reductant and the requirement of a directing group limit the application of transition metal-catalyzed reductive difunctionalization of alkenes with alkyl halides. Here, the authors report a reductive difunctionalization of alkenes via a radical-anion relay with Na2S2O4 as both reductant and sulfone-source.[ASAP] Dual Photoredox/Cobalt-Catalyzed Reductive Cyclization of Alkynals
Biocatalytic strategy for the construction of sp3-rich polycyclic compounds from directed evolution and computational modelling
BracaFrom 0 to 99 in just 4 seco... khm mutations.
Nature Chemistry, Published online: 13 February 2024; doi:10.1038/s41557-023-01435-3
The use of biocatalysis to support early-stage drug discovery campaigns remains largely untapped. Here, engineered biocatalysts enable the synthesis of sp3-rich polycyclic compounds through an intramolecular cyclopropanation of benzothiophenes, affording a class of complex scaffolds potentially useful for fragment-based drug discovery campaigns.Selective Aza‐Michael Addition to Dehydrated Amino Acids in Natural Antimicrobial Peptides
Antimicrobial resistance is an urgent global public health problem that has made the search for new antibiotics essential. Ribosomally synthesized and post-translationally modified peptides are a promising new class of antibiotics and in this work, we report site-selective modification of their dehydroamino acids by β-amination in order to increase water solubility: the singly modified thiopeptide Thiostrepton showed an increase up to 35-fold and minimum inhibitory concentration tests demonstrated that the antimicrobial activity was still good, albeit lower than the natural peptide.
Abstract
We report the efficient and site selective modification of non-canonical dehydroamino acids in ribosomally synthesized and post-transationally modified peptides (RiPPs) by β-amination. The singly modified thiopeptide Thiostrepton showed an up to 35-fold increase in water solubility, and minimum inhibitory concentration (MIC) assays showed that antimicrobial activity remained good, albeit lower than the unmodified peptide. Also the lanthipeptide nisin could be modified using this method.