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Not AvailableAn unmet challenge in radical relay difunctionalization of alkenes is incorporation of two discrete transient radicals in a regiocontrolled manner under transition metal-free conditions. Current protocols typically rely on persistent radicals or organometallic surrogates to trap radical adducts, thereby suppressing the undesired reactions but limiting the diversity. The direct use of two transient radicals remains synthetically elusive. We present a visible-light photoredox catalyzed alkene dialkylation strategy via a kinetically guided conjugative radical-radical coupling. This transition-metal-free approach enables two direct C(sp3)−C(sp3) bond formations across the C=C double bond using alkyl and allyl or benzyl radicals. Mechanistic investigations reveal the radical nature of the process. The success of this approach hinges on kinetically controlled radical addition to alkene substrates and the steric protection of the resulting radical adducts. This mild and functional-group tolerant reaction exhibits broad substrate scope and tolerates structurally complex substrates, highlighting its potential for late-stage functionalization. 

Abstract Carbosulfenylation of olefins represents an important class of reactions for the synthesis of structurally diverse organosulfur compounds. Previous studies typically yield 1,2‐regioselectivity. In the context of diversity‐oriented synthesis, accessing the regioreversed products is desirable, significantly broadening the scope of these reactions. In this study, we report a nickel‐catalyzed 2,1‐carbosulfenylation of trifluoromethyl‐ andgem‐difluoroalkenes, using free thiols and benzyl bromides as sulfur and carbon sources, respectively. The unusual regioselectivity observed is enabled by a “radical sorting” mechanism. The Ni catalyst activates benzyl bromide to generate a benzylic radical that undergoes hydrogen atom transfer (HAT) with the thiol to form a sulfur‐centered radical. The sulfur radical subsequently adds to the fluoroalkenes, resulting in an α‐fluoroalkyl C‐radical. This radical undergoes S_H2 with a Ni–CH₂Ar to form a C(sp³)─C(sp³) bond and quaternary center, ultimately producing valuable fluoroalkyl thioethers. Isotopic labeling experiments corroborate a hydrogen atom transfer (HAT) event within the working mechanism. 

Abstract Nanomaterial‐based stretchable electronics composed of conductive nanomaterials in elastomer can seamlessly integrate with human skin to imperceptibly capture electrophysiological signals. Despite the use of transfer printing to form embedded structures, it remains challenging to facilely and stably integrate conductive nanomaterials with thin, low‐modulus, adhesive elastomers. Here, a facile‐yet‐simple laser‐induced graphene (LIG)‐assisted patterning and transfer method is demonstrated to integrate patterned silver nanowires onto an ultra‐low modulus silicone adhesive as ultra‐conformal epidermal electrodes. The resulting thin epidermal electrodes of ≈50 µm exhibit a low sheet resistance (0.781 Ω sq⁻¹), tissue‐like Young's modulus (0.53 MPa), strong self‐adhesion, and excellent breathability. The breathable electrodes dynamically conformed to the skin with low contact impedance allow for long‐term, high‐fidelity monitoring of electrophysiological signals in complex environments (even during exercise and heavy sweating). Moreover, the LIG‐assisted transfer can provide a robust interface to establish a stable connection between the soft electrodes and rigid hardware. The large‐scale fabrication further provides an eight‐channel electromyography system combined with a deep learning algorithm for gesture classification and recognition with remarkable accuracy (95.4%). The results from this study also provide design guidelines and fabrication methods of the next‐generation epidermal electronics for long‐term dynamic health monitoring, prosthetic control, and human‐robot collaborations.