Generating alkyl carbanions for organic synthesis
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C(sp3)–heteroatom bond formation by iron-catalyzed soft couplings
Carbon–heteroatom bonds are of great importance due to their prevalence in pharmaceuticals, agrochemicals, materials, and natural products. Despite the effective use of metal-catalyzed cross-coupling reactions between sp2-hybridized organohalides and soft heteroatomic nucleophiles for carbon–heteroatom bond formation, the use of sp3-hybridized organohalides remain limited and the coupling with thiols remains elusive. Here, we report the coupling of sp3-hybridized benzyl or tertiary halides with soft thiol nucleophiles catalyzed by iron and extend the utility to alcohol and amine nucleophiles. The reaction is broad in substrate scope for both coupling partners and applicable in the construction of congested tri- and tetrasubstituted carbon centers as well as β-quaternary heteroatomic products. The synthetic utility is further emphasized by gram-scale synthesis and rapid herbicide library synthesis. Overall, we provide an efficient method to prepare pharmaceutically and materially relevant carbon–heteroatom bonds by expanding iron-catalyzed cross-coupling reactions to the coupling of sp3-hybridized organohalides with soft nucleophiles.
Chemical linkers switch triglycerol detergents from bacterial protein purification to mild antibiotic amplification
Non-ionic detergents enable the investigation of cell membranes, including biomolecule purification and drug delivery. The question of whether non-ionic detergents associated with satisfying protein yields following extraction and affinity purification of proteins from lysed E. coli membranes can amplify antibiotics on whole-cell E. coli remains to be addressed. We unlock the modular chemistry of linear triglycerol detergents to reveal that more polar, non-ionic detergents that form globular micelles work better in amplifying antimicrobial activities of antibiotics than in purifying the membrane proteins mechanosensitive channel and aquaporin Z. Less polar detergents that form worm-like micelles indicate poor performances in both applications. With chromatography we demonstrate how fine-tuning the polarity of chemical linkers between detergent headgroups and tails can switch the utility of detergents from protein purification to antibiotic amplification. We anticipate our findings to be a starting point for structure-property studies to better understand detergent designs in supramolecular chemistry and membrane research.
A robust organic hydrogen sensor for distributed monitoring applications
Hydrogen is an abundant and clean energy source that could help to decarbonize difficult-to-electrify economic sectors. However, its safe deployment relies on the availability of cost-effective hydrogen detection technologies. We describe a hydrogen sensor that uses an organic semiconductor as the active layer. It can operate over a wide temperature and humidity range. Ambient oxygen p-dopes the organic semiconductor, which improves hole transport, and the presence of hydrogen reverses this doping process, leading to a drop in current and enabling reliable and rapid hydrogen detection. The sensor exhibits a high responsivity (more than 10,000), fast response time (less than 1 s), low limit of detection (around 192 ppb) and low power consumption (less than 2 μW). It can operate continuously for more than 646 days in ambient air at room temperature. We show that the sensor outperforms a commercial hydrogen detector in realistic sensing scenarios, illustrating its suitability for application in distributed sensor networks for early warning of hydrogen leaks and preventing explosions or fires.
Pilot-scale partial nitrification and anaerobic ammonium oxidation system for nitrogen removal from municipal wastewater
Partial nitrification has the advantages of saving energy and reducing the need for carbon sources in municipal wastewater treatment. However, for municipal wastewater with low ammonia, start-up and maintenance of partial nitrification is a worldwide challenge. Here we developed a pilot-scale double sludge system consisting of two sequencing batch reactors for partial nitrification (12 m2) and denitrification/anaerobic ammonium oxidation (denitrification/anammox, 8.4 m2) to treat municipal wastewater. Partial nitrification was maintained at no ammonium remaining with a nitrite accumulation rate of 87.7%. This study found that partial nitrification system effluent chemical oxygen demand increased from 24.8 mg L−1 to 64.9 mg L−1 accompanied by transformation from complete nitrification to partial nitrification. In the denitrification/anammox system, the reduction of nitrite to nitrogen required about 40% less carbon consumption than nitrate. High nitrogen removal was achieved with effluent total inorganic nitrogen of 2.7 mg L−1 without carbon addition. This work provided a pilot-scale demonstration of low-carbon high-nitrogen removal.
Biomimetic 1,2-amino migration via photoredox catalysis
Synthetic organic chemists continually draw inspiration from biocatalytic processes to innovate synthetic methodologies beyond existing catalytic platforms. Within this context, although 1,2-amino migration represents a viable biochemical process, it remains underutilized within the synthetic organic chemistry community. Here we present a biomimetic 1,2-amino migration accomplished through the synergistic combination of biocatalytic mechanism and photoredox catalysis. This platform enables the modular synthesis of γ-substituted β-amino acids by utilizing abundant α-amino-acid derivatives and readily available organic molecules as coupling partners. This mild method features excellent substrate and functionality compatibility, affording a diverse range of γ-substituted β-amino acids (more than 80 examples) without the need for laborious multistep synthesis. Mechanistic studies, supported by both experimental observations and theoretical analysis, indicate that the 1,2-amino migration mechanism involves radical addition to α-vinyl-aldimine ester, 3-exo–trig cyclization and a subsequent rearrangement process. We anticipate that this transformation will serve as a versatile platform for the highly efficient construction of unnatural γ-substituted β-amino acids.
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