Articles

Filter By:

Article Type
  • Alkane carbonylation through photocatalytic alkyl radical addition to CO is a challenge. Now, an equilibrium-leveraging strategy which combines the direct carbonylation of alkanes with CO with onwards enantioselective transformations is reported, providing an enantioselective method for the synthesis of β-amino and α-amino ketones.

    • Wei-Wei Ding
    • Zhi-Yuan He
    • Liu-Zhu Gong
    Article
  • The catalytic carboxylation of C(sp2)–H bonds using CO2 is an efficient strategy to produce carboxylic acids; however, the carboxylation of azines is a challenge. Now, a visible-light-driven, thiolate-catalysed method for the carboxylation of azine C(sp2)–H bonds using CO2 is reported, enabling the synthesis of N-heteroaromatic carboxylic acids with excellent regiocontrol.

    • Yuan-Xu Jiang
    • Li-Li Liao
    • Da-Gang Yu
    Article
  • The use of a universal chemical programming language (χDL) to encode and execute synthesis procedures for a variety of chemical reactions is reported, including reductive amination, ring formation, esterification, carbon–carbon bond formation and amide coupling. These procedures are validated and repeated in two international laboratories and on three independent robots.

    • Robert Rauschen
    • Mason Guy
    • Leroy Cronin
    Article
  • Acid-triggered reversible addition–fragmentation chain-transfer polymerizations, in the absence of conventional initiating species and in the dark, are reported to prepare polymers with low dispersity and high end-group fidelity. The protonation of monomers catalyses both the initiation and propagation steps and can also be applied to free radical polymerizations.

    • Maria-Nefeli Antonopoulou
    • Glen R. Jones
    • Athina Anastasaki
    ArticleOpen Access
  • Homologation of organoboronates by iterative carbenoid insertion is an effective method for the synthesis of alkyl chains, but the corresponding homologation using vinyl units remains elusive. Now, a stereoselective vinylene homologation reaction is reported, comprising diastereoselective successive insertion of silyl- and alkoxy-substituted carbenoids into organoboronates, followed by a Peterson-type elimination.

    • Miao Chen
    • Thomas H. Tugwell
    • Guangbin Dong
    Article
  • Chiral α-quaternary amino and glycolic acids have found use in medicinal applications. Although their synthesis through α-alkylation is well known, synthesis via α-arylation remains challenging. Now, palladium-catalysed methods for the enantioselective α-arylation of amino acid- and glycolic acid-derived heterocycles, azlactones and 5H-oxazol-4-ones, using aryl bromides, are reported.

    • Shutao Qi
    • Wenshao Ye
    • Junliang Zhang
    Article
  • The use of gaseous sulfuryl fluoride in sulfur(VI) fluoride exchange reactions is a challenge. Now, a flow set-up for the on-demand generation and onward reaction of sulfuryl fluoride, from sulfuryl chloride, is reported. The process produces fluorosulfate and sulfamoyl fluoride analogues of small molecules, peptides and proteins.

    • Miguel Bernús
    • Daniele Mazzarella
    • Timothy Noël
    Article
  • Water electrolysis can produce clean hydrogen, but it is limited by the slow anodic oxygen evolution reaction. Now, a local electronic manipulation strategy for stabilizing high-valence Ru single site catalysts has been developed. The catalyst demonstrates efficient bifunctional activity for water electrolysis.

    • Shi-Yu Lu
    • Bolong Huang
    • Shaojun Guo
    Article
  • Cation–anion exchange between dimers to prepare mixed aggregates with Mg–Ae (alkaline earth) bonding (Ae = Mg, Ca, Sr, Ba) is reported. Considerable electron transfer from the (BDI)Mgˉ anion (BDI, β-diketiminate) to Ae and Na atoms is observed, and the reactivity of these electron-rich complexes with Na–Mg–Ae bonding is discussed.

    • Jonathan Mai
    • Johannes Maurer
    • Sjoerd Harder
    Article
  • Nimbolide is an inhibitor of poly(ADP)-ribosylation-dependent ubiquitin E3 ligase RNF114. A modular synthesis of nimbolide and its analogues is now reported, using a sulfonyl hydrazone-mediated etherification and a radical cyclization strategy. These analogues give insight into structure–activity relationships and some have superior poly(ADP-ribose) polymerase-1 trapping activity relative to nimbolide.

    • Heping Deng
    • Hejun Deng
    • Tian Qin
    Article
  • The unexpected phenomenon of rapid, long-distance transport of an ultrathin and uniform metal film on two-dimensional crystals is reported at temperatures well below the melting points of all of the materials involved. The effect is generalizable and may offer possibilities in confined space chemistry, as well as in two-dimensional crystal growth and devices.

    • Yanyu Jia
    • Fang Yuan
    • Sanfeng Wu
    Article
  • A flow microreactor-enabled method is reported for the stereo- and regioselective synthesis of multisubstituted alkenes by reductive syn-boryllithiation and syn-borylsodiation of arylacetylenes. Reaction of the alkyne substrate with a naphthalenide reductant and a boron electrophile generates a syn-β-borylalkenyl alkali metal intermediate, which can react with a range of electrophiles.

    • Yiyuan Jiang
    • Takashi Kurogi
    • Hideki Yorimitsu
    ArticleOpen Access
  • Sustained Mars exploration requires in situ synthesis of vital chemicals such as oxygen. Now a data-driven platform for synthesizing oxygen-producing electrocatalysts from Martian meteorites using robotics and artificial intelligence is developed, allowing automated screening of the optimal catalyst formula. This approach demonstrates materials discovery under challenging circumstances and without human intervention.

    • Qing Zhu
    • Yan Huang
    • Yi Luo
    Article
  • The chemical synthesis of jasmonates is typically low yielding and can be laborious, whereas their extraction can be costly or environmentally hazardous. Now a de novo biosynthesis of jasmonic acid and its derivatives, methyl jasmonate and jasmonoyl isoleucine, is reported, using an engineered baker’s yeast.

    • Hongting Tang
    • Shumin Lin
    • Xiaozhou Luo
    Article
  • Strained cyclic allenes are short-lived intermediates that confine a functional group with a preferred linear geometry, an allene, into a small ring, inducing strain-driven reactivity. Now, 2,3-azacyclic and 2,3-oxacyclic allenes are generated and trapped using cycloaddition reactions, generating complex heterocycles that bear a large fraction of sp3-hybridized atoms.

    • Andrew V. Kelleghan
    • Arismel Tena Meza
    • Neil K. Garg
    Article