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Article
Open AccessWhy •CF2H is nucleophilic but •CF3 is electrophilic in reactions with heterocycles
Radical substitution is a useful method to functionalize heterocycles, as in the venerable Minisci reaction. Empirically observed regiochemistries indicate that the CF2H radical has a nucleophilic character simil...
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Article
Biocatalytic, enantioenriched primary amination of tertiary C–H bonds
Intermolecular functionalization of tertiary C–H bonds to construct fully substituted stereogenic carbon centres represents a formidable challenge: without the assistance of directing groups, state-of-the-art ...
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Article
Biocatalytic strategy for the construction of sp3-rich polycyclic compounds from directed evolution and computational modelling
Catalysis with engineered enzymes has provided more efficient routes for the production of active pharmaceutical agents. However, the potential of biocatalysis to assist in early-stage drug discovery campaigns...
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Article
Biocatalytic, stereoconvergent alkylation of (Z/E)-trisubstituted silyl enol ethers
The selective conversion of mixtures of Z/E alkenes into chiral products is a synthetic challenge. Biocatalytic strategies can transform isomeric alkenes into stereopure compounds, but enzymes typically convert o...
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Article
Modular synthesis of 1,2-azaborines via ring-opening BN-isostere benzannulation
1,2-Azaborines represent a unique class of benzene isosteres that have attracted interest for develo** pharmaceuticals with better potency and bioavailability. However, it remains a long-standing challenge t...
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Article
Stereoselective construction of β-, γ- and δ-lactam rings via enzymatic C–H amidation
Lactam rings are found in many biologically active natural products and pharmaceuticals, including important classes of antibiotics. Methods for the asymmetric synthesis of these molecules are therefore highly...
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Article
Open AccessAtroposelective hydroarylation of biaryl phosphines directed by phosphorus centres
Prized for their ability to generate chemical complexity rapidly, catalytic carbon–hydrogen (C–H) activation and functionalization reactions have enabled a paradigm shift in the standard logic of synthetic che...
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Article
Tandem intermolecular [4 + 2] cycloadditions are catalysed by glycosylated enzymes for natural product biosynthesis
Tandem Diels–Alder reactions are frequently used in the construction of polycyclic ring systems in complex organic compounds. Unlike the many Diels−Alderases (DAases) that catalyse a single cycloaddition, enzy...
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Article
Achieving sustainability of greenhouses by integrating stable semi-transparent organic photovoltaics
Semi-transparent organic photovoltaics (OPVs) are an emerging solar-energy-harvesting technology with promising applications, such as rooftop energy supplies for environmentally friendly greenhouses. However, ...
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Article
An NmrA-like enzyme-catalysed redox-mediated Diels–Alder cycloaddition with anti-selectivity
The Diels–Alder cycloaddition is one of the most powerful approaches in organic synthesis and is often used in the synthesis of important pharmaceuticals. Yet, strictly controlling the stereoselectivity of the...
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Article
Open AccessArene C–H borylation strategy enabled by a non-classical boron cluster-based electrophile
Introducing a tri-coordinate boron-based functional group (e.g., boronic ester) into an unactivated C–H bond in the absence of directing groups is an ongoing challenge in synthetic chemistry. Despite previous ...
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Article
Nickel-catalysed regio- and stereoselective acylzincation of unsaturated hydrocarbons with organozincs and CO
Carbometallation of unsaturated hydrocarbons is one of the most straightforward functionalizations of carbon–carbon unsaturated bonds; however, the analogous acylmetallation remains a significant synthetic cha...
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Article
Open AccessDe novo design of luciferases using deep learning
De novo enzyme design has sought to introduce active sites and substrate-binding pockets that are predicted to catalyse a reaction of interest into geometrically compatible native scaffolds1,2, but has been limit...
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Article
A cyclase that catalyses competing 2 + 2 and 4 + 2 cycloadditions
Cycloaddition reactions are among the most widely used reactions in chemical synthesis. Nature achieves these cyclization reactions with a variety of enzymes, including Diels–Alderases that catalyse concerted ...
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Article
Mechanistic and structural characterization of an iridium-containing cytochrome reveals kinetically relevant cofactor dynamics
Artificial metalloenzymes (ArMs), which contain non-native, typically synthetic, metal cofactors, are a flourishing class of biocatalyst for unnatural reactions. Although the number of these reactions is rapid...
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Article
Open AccessHow mono- and diphosphine ligands alter regioselectivity of the Rh-catalyzed annulative cleavage of bicyclo[1.1.0]butanes
Rh(I)-catalyzed cycloisomerizations of bicyclo[1.1.0]butanes provide a fruitful approach to cyclopropane-fused heterocycles. Products and stereochemical outcome are highly dependent on catalyst. The triphenylp...
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Article
Open AccessOxygen mediated oxidative couplings of flavones in alkaline water
Catalyzed oxidative C-C bond coupling reactions play an important role in the chemical synthesis of complex natural products of medicinal importance. However, the poor functional group tolerance renders them unfi...
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Article
Molecular editing of aza-arene C–H bonds by distance, geometry and chirality
Direct molecular editing of heteroarene carbon–hydrogen (C–H) bonds through consecutive selective C–H functionalization has the potential to grant rapid access into diverse chemical spaces, which is a valuable...
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Article
Open AccessPrecise electrical gating of the single-molecule Mizoroki-Heck reaction
Precise tuning of chemical reactions with predictable and controllable manners, an ultimate goal chemists desire to achieve, is valuable in the scientific community. This tunability is necessary to understand ...
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Article
Lattice strain suppresses point defect formation in halide perovskites
We computationally investigate the impact of crystal strain on the formation of native point defects likely to be formed in halide perovskites; A-site cation antisite (IA), Pb antisite (IPb), A-site cation vacany...
