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Plasmon‐Enhanced InGaZnO Ultraviolet Photodetectors Tuned by Ferroelectric HfZrO
摘要: Allene (C3H4) gas is produced and separated on million-metric-ton scale per year during petroleum refining but is rarely employed in organic synthesis. Meanwhile, the addition of an allyl group (C3H5) to ketones is among the most common and prototypical reactions in synthetic chemistry. Herein, we report that the combination of allene gas with inexpensive and environmentally benign hydrosilanes, such as PMHS, can serve as a replacement for stoichiometric quantities of allylmetal reagents, which are required in most enantioselective ketone allylation reactions. This process is catalyzed by copper salts and commercially available ligands, operates without specialized equipment or pressurization, and tolerates a broad range of functional groups. Furthermore, the exceptional chemoselectivity of this catalyst system enables industrially relevant C3 hydrocarbon mixtures of allene with methylacetylene and propylene to be applied directly.
关键词: enantioselective allylation,allene,copper catalysis,hydrosilanes,petroleum cracking byproduct,ketones
更新于2025-09-19 17:13:59
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Photo‐Organocatalytic Enantioselective Radical Cascade Enabled by Single‐Electron Transfer Activation of Allenes
摘要: Allenes are commonly used in metal-mediated transformations, cycloaddition reactions, and radical processes. However, their activation by single-electron transfer (SET) is largely underexplored. Herein, we report a visible light-driven enantioselective organocatalytic process that uses the excited-state reactivity of chiral iminium ions to activate allenes by SET oxidation. The ensuing allene cation radicals participate in stereocontrolled cascade reactions to deliver bicyclic scaffolds with good enantioselectivity and exquisite diastereoselectivity. Density Functional Theory (DFT) calculations support a mechanism that combines the peculiar chemistry of allene radical cations with polar reactivity.
关键词: photochemistry,cascade process,allene,enantioselective organocatalysis,radical chemistry
更新于2025-09-19 17:13:59