Azidation of alkenes is an efficient protocol to synthesize organic azides which are important structural motifs in organic synthesis. Enantioselective radical azidation, as a useful strategy to install a C−N 3 bond, remains challenging due to the inherently instability and unique structure of radicals. Here, we disclose an efficient enantioselective radical carboazidation and diazidation of α,β-unsaturated ketones and amides catalyzed by chiral N,N′-dioxide/Fe(OTf) 2 complexes. An array of substituted alkenes was transformed to the corresponding α-azido carbonyl derivatives in good to excellent enantioselectivities, benefiting the preparation of chiral α-amino ketones, vicinal amino alcohols, and vicinal diamines. Control experiments and mechanistic studies proved the radical pathway in the reaction process. The DFT calculations showed that the azido transferred to the radical intermediate via an intramolecular five-membered transition state with the internal nitrogen of the Fe−N 3 species.

Aiming at the serious problems caused by coal mine mining activities causing the rock burst accidents, this paper is based on rock mechanics and material mechanics to establish the key layer breaking by the double-key layer beam breaking structural mechanics model of a single working face and double working face under repeated mining. The theoretical calculation formula of the angle was used as the theoretical basis for the elevation angle of the pre-reloading hole of the hard roof. The rationality and reliability of the formula were verified by the physical similarity simulation experiment and the 3 Dimension Distinct Element Code numerical simulation experiment, revealing the rock formation under the influence of repeated mining. The results show that the derived key layer breaking angle formula is suitable for the theoretical calculation of the breaking angle of the key layer of a single coal seam when the repeated disturbance coefficient is λ = 1; when it is λ = 2, it is suitable for the repeated mining of the short-distance double-coal mining. The rationality and reliability of the theoretical formula of the breaking angle of the double key layer of single coal seam and double coal seam were verified by the physical similarity simulation experiment. Through the 3DEC numerical simulation results and theoretical calculation results, the W1123 working face hard top pre-cracking pressure relief drilling elevation angle was 78°. The drilling peeping method was used to verify the results. The results show that the theoretical formula of the critical layer breaking angle is well applied in engineering practice.

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