Despite the observation of noncovalent interactions between chalcogen atoms in X-ray crystal structures, catalysis that harnesses the power of such chalcogen−chalcogen bonding interactions to produce advanced molecules remains an unresolved problem. Here, we show that a class of extraordinary chalcogenbonding catalysts enables assembly of discrete small molecules including three β-ketoaldehydes and one indole, leading to the construction of N-heterocycles in a highly efficient manner. The strong activation ability of these rationally designed catalysts provides a general solution to the intrinsic limitations of chalcogen bonding catalysis.
The noncovalent S···O
bonding interaction is an
evolutionary force that has been smartly exploited by nature to modulate
the conformational preferences of proteins. The employment of this
type of weak noncovalent force to drive chemical reactions is promising
yet remains largely elusive. Herein, we describe a dual chalcogen–chalcogen
bonding catalysis strategy that the distinct chalcogen atoms simultaneously
interact with two chalcogen-based electron donors to give rise to
the catalytic activity, thus facilitating chemical reactions. Conventional
approaches to the Rauhut–Currier-type reactions require the
use of strongly nucleophilic Lewis bases as essential promoters. The
implementation of this dual chalcogen–chalcogen bonding catalysis
strategy allows the simultaneous Se···O bonding interaction
between chalcogen-bonding donors and an enone and an alcohol, enabling
the realization of the Rauhut–Currier-type reactions in a distinct
way. The further implementation of a consecutive dual Se···O
bonding catalysis approach enables the achievement of an initial Rauhut–Currier-type
reaction to give an enone product which further undergoes an alcohol-addition
induced cyclization reaction. This work demonstrates that the nearly
linear chalcogen-bonding interaction can differentiate similar alkyl
groups to give rise to regioselectivity. Moreover, the new strategy
shows its advantage as it not only enables less reactive substrates
working efficiently but tolerates inaccessible substrates using conventional
methods.
Non-dispersive infrared (NDIR) spectroscopy analyzes the concentration of target gases based on their characteristic infrared absorption. In conventional NDIR gas sensors, an infrared detector has to pair with a bandpass filter to select the target gas. However, multiplexed NDIR gas sensing requires multiple pairs of bandpass filters and detectors, which makes the sensor bulky and expensive. Here, we propose a multiplexed NDIR gas sensing platform consisting of a narrowband infrared detector array as read-out. By integrating plasmonic metamaterial absorbers with pyroelectric detectors at the pixel level, the detectors exhibit spectrally tunable and narrowband photoresponses, circumventing the need for separate bandpass filter arrays. We demonstrate the sensing of H2S, CH4, CO2, CO, NO, CH2O, NO2, SO2. The detection limits of common gases such as CH4, CO2, and CO are 63 ppm, 2 ppm, and 11 ppm, respectively. We also demonstrate the deduction of the concentrations of two target gases in a mixture.
The activation of aziridines typically involves the use of strong Lewis acids or transition metals, and methods relying on weak interactions are rare. Herein, we report that cooperative chalcogen bonding interactions in confined sites can activate sulfonyl-protected aziridines. Among the several possible distinct bonding modes, our experiments and computational studies suggest that an activation mode involving the cooperative Se···O and Se···N interactions is in operation. The catalytic reactions between weakly bonded supramolecular species and nonactivated alkenes are considered as unfavorable approaches. However, here we show that the activation of aziridines by cooperative Se···O and Se···N interactions enables the cycloaddition of weakly bonded aziridine-selenide complex with nonactivated alkenes in a catalytic manner. Thus, weak interactions can indeed enable these transformations and are an alternative to methods relying on strong Lewis acids.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.