Given the unique charm of dipole chemistry, intercepting N−O=C dipoles precisely generated by designed processes to develop novel reactivity has become a seminal challenge. The polar fragmentation of 1,3,2‐dioxazolidine species generated through the radical addition of excited nitro(hetero)arenes to alkenes represents a significantly underappreciated mechanism for generating N−O=C dipoles. Herein, we present a photoinduced Bartoli indole synthesis by the oxidative cleavage of alkenes with nitro(hetero)arenes. Various indoles and azaindoles are constructed through the multi‐step spontaneous rearrangement of carbonyl imine intermediates generated by the polar fragmentation of 1,3,2‐dioxazolidine species. Mechanism studies and DFT calculations support that the reaction involves radical cycloaddition, ozonolysis‐type cycloreversion, intramolecular H‐shift of carbonyl imines, and 3,3‐sigmatropic shift of O‐Alkenyl hydroxylamines, etc. The implementation of continuous‐ flow photochemistry, in particular, significantly enhances efficiency, thereby overcoming obstacles to the commercialization process.
The influence of varying the manganese (Mn) contents of high-strength copper-containing hull steel on its microstructural evolution and mechanical properties was investigated. With increasing Mn content from 2 to 5%, the tensile strength of the steel increased by ~100 MPa, while the elongation of steel remained at ~23.5%, indicating good plasticity. However, the 2Mn sample had 128 J higher low-temperature (−84 °C) impact work than the 5Mn sample. The microstructures of different Mn steels were composed of fresh martensite (FM), ferrite/tempered martensite (F/TM), and reversed austenite (RA). The increase in Mn content markedly increased the presence of RA and intensified the work hardening caused by the transformation-induced plasticity (TRIP) effect during the tensile process. However, as the phase transformation in different Mn steels occurred in the early stage of strain and did not extend throughout the entire plastic deformation process, increasing plasticity via phase transformation was difficult. In addition, although the volume fraction of RA increased significantly in 4Mn and 5Mn steels, the stability of RA significantly decreased. The presence of numerous metastable blocks and coarse lath-like RA contributed little to low-temperature impact work and was even detrimental to toughness. The substantial fresh martensite resulting from phase transformation facilitated microcrack generation, owing to rapid volume expansion and mutual impacts, thus reducing the work required for crack formation. Additionally, the abundance of deformation twins significantly reduced the work needed for crack propagation. These combined actions significantly reduced the low-temperature toughness of 4Mn and 5Mn steels.
21 January 2023 in Materials Science and Engineering: A