Despite advances in hydrogen atom transfer (HAT) catalysis, there are currently no molecular HAT catalysts that are capable of homolysing the strong nitrogen-hydrogen (N-H) bonds of N-alkyl amides. ...The motivation to develop amide homolysis protocols stems from the utility of the resultant amidyl radicals, which are involved in various synthetically useful transformations, including olefin amination and directed carbon-hydrogen (C-H) bond functionalization. In the latter process-a subset of the classical Hofmann-Löffler-Freytag reaction-amidyl radicals remove hydrogen atoms from unactivated aliphatic C-H bonds. Although powerful, these transformations typically require oxidative N-prefunctionalization of the amide starting materials to achieve efficient amidyl generation. Moreover, because these N-activating groups are often incorporated into the final products, these methods are generally not amenable to the direct construction of carbon-carbon (C-C) bonds. Here we report an approach that overcomes these limitations by homolysing the N-H bonds of N-alkyl amides via proton-coupled electron transfer. In this protocol, an excited-state iridium photocatalyst and a weak phosphate base cooperatively serve to remove both a proton and an electron from an amide substrate in a concerted elementary step. The resultant amidyl radical intermediates are shown to promote subsequent C-H abstraction and radical alkylation steps. This C-H alkylation represents a catalytic variant of the Hofmann-Löffler-Freytag reaction, using simple, unfunctionalized amides to direct the formation of new C-C bonds. Given the prevalence of amides in pharmaceuticals and natural products, we anticipate that this method will simplify the synthesis and structural elaboration of amine-containing targets. Moreover, this study demonstrates that concerted proton-coupled electron transfer can enable homolytic activation of common organic functional groups that are energetically inaccessible using traditional HAT-based approaches.
A versatile method for the hydromethylation and hydroalkylation of alkenes at room temperature is achieved by using the photooxidative redox capacity of the valence band of anatase titanium dioxide ...(TiO2). Mechanistic studies support a radical-based mechanism involving the photoexcitation of TiO2 with 390 nm light in the presence of acetic acid and other carboxylic acids to generate methyl and alkyl radicals, respectively, without the need for stoichiometric base. This protocol is accepting of a broad scope of alkene and carboxylic acids, including challenging ones that produce highly reactive primary alkyl radicals and those containing functional groups that are susceptible to nucleophilic substitution such as alkyl halides. This methodology highlights the utility of using heterogeneous semiconductor photocatalysts such as TiO2 for promoting challenging organic syntheses that rely on highly reactive intermediates.
Chlorine radicals readily activate C–H bonds, but the high reactivity of these intermediates precludes their use in regioselective C–H functionalization reactions. We demonstrate that the secondary ...coordination sphere of a metal complex can confine photoeliminated chlorine radicals and afford steric control over their reactivity. Specifically, a series of iron(III) chloride pyridinediimine complexes exhibit activity for photochemical C(sp3)–H chlorination and bromination with selectivity for primary and secondary C–H bonds, overriding thermodynamic preference for weaker tertiary C–H bonds. Transient absorption spectroscopy reveals that Cl· remains confined through formation of a Cl·|arene complex with aromatic groups on the pyridinediimine ligand. Furthermore, photocrystallography confirms that this selectivity arises from the generation of Cl· within the steric environment defined by the iron secondary coordination sphere.
The direct, site-selective alkylation of unactivated C(sp3)–H bonds in organic substrates is a long-standing goal in synthetic chemistry. General approaches to the activation of strong C–H bonds ...include radical-mediated processes involving highly reactive intermediates, such as heteroatom-centered radicals. Herein, we describe a catalytic, intermolecular C–H alkylation that circumvents such reactive species via a new elementary step for C–H cleavage involving multisite-proton-coupled electron transfer (multisite-PCET). Mechanistic studies indicate that the reaction is catalyzed by a noncovalent complex formed between an iridium(III) photocatalyst and a monobasic phosphate base. The C–H alkylation proceeds efficiently using diverse hydrocarbons and complex molecules as the limiting reagent and represents a new approach to the catalytic functionalization of unactivated C(sp3)–H bonds.
A new catalytic method is described to access carbocation intermediates via the mesolytic cleavage of alkoxyamine radical cations. In this process, electron transfer between an excited state oxidant ...and a TEMPO‐derived alkoxyamine substrate gives rise to a radical cation with a remarkably weak C−O bond. Spontaneous scission results in the formation of the stable nitroxyl radical TEMPO. as well as a reactive carbocation intermediate that can be intercepted by a wide range of nucleophiles. Notably, this process occurs under neutral conditions and at comparatively mild potentials, enabling catalytic cation generation in the presence of both acid sensitive and easily oxidized nucleophilic partners.
Carbocation intermediates can be accessed by mesolytic cleavage of alkoxyamine radical cations with a remarkably weak C−O bond. Spontaneous scission results in the formation of the stable nitroxyl radical TEMPO. and the reactive carbocation intermediate that can be intercepted by a wide range of nucleophiles.
Abstract Background Cancer and sarcopenia are both closely related to lipid metabolism, but the relationship between lipid metabolism and patients with cancer and sarcopenia has not been thoroughly ...studied. The non-high-density lipoprotein cholesterol to high-density lipoprotein cholesterol ratio (NHHR) is a reliable measure of lipid metabolism. The purpose of this study was to determine the possible relationship between the NHHR and sarcopenia in individuals with cancer. Methods Data from the National Health and Nutrition Examination Survey (NHANES) database for individuals with cancer, with and without sarcopenia was analyzed using weighted multiple regression equations, weighted regression cubic spline (RCS) analysis, and weighted subgroup analysis. Results In total, 1,602 individuals with cancer were included, of whom 17.1% had sarcopenia. In Adjusted Model 2, the occurrence of sarcopenia was found to be significantly associated with a higher NHHR in cancer (95% confidence interval CI:1.01–1.39, P = 0.036). Individuals with high a NHHR had a 2.09-fold higher risk of developing sarcopenia in comparison to those with a low NHHR (95% CI:1.12–3.92, P = 0.022). RCS analysis further identified a U-shaped non-linear relationship between females with cancer and the muscle index. Subgroup analysis indicated that sex was a significant stratifying factor, whereas age, race, marital status, smoking and drinking habits, and history of cardiovascular disease, arthritis, hypertension, and diabetes had no significant impact. Conclusion From the perspective of lipid metabolism, the NHHR may serve as an indicator for monitoring and preventing the occurrence of sarcopenia in individuals with cancer, particularly for females with cancer who appear to have greater sensitivity.
Crop residue is an important component of farmland ecosystems, which is of great significance for increasing soil organic carbon, mitigating wind erosion and water erosion and conserving soil and ...water. Crop residue coverage (CRC) is an important parameter to characterize the number and distribution of crop residues, and also a key indicator of conservation tillage. In this study, the CRC of wheat was taken as the research object. Based on the high-resolution GF-1 satellite remote sensing imagery from China, decision tree (DT), gradient boosting decision tree (GBDT), random forest (RF), least absolute shrinkage and selection operator (LASSO), extreme gradient boosting regression (XGBR) and other machine learning algorithms were used to carry out the estimation of wheat CRC by remote sensing. In addition, the comparisons with sentinel-2 imagery data were also utilized to assess the potential of GF satellite data for CRC estimates. The results show the following: (1) Among the spectral indexes using shortwave infrared characteristic bands from sentinel-2 imagery, the dead fuel index (DFI) was the best for estimating wheat CRC, with an R2 of 0.54 and an RMSE of 10.26%. The ratio vegetation index (RVI) extracted from visible and near-infrared characteristic bands from GF-1 data performed the best, with an R2 of 0.46 and an RMSE of 11.39%. The spectral index extracted from GF-1 and sentinel-2 images had a significant response relationship with wheat residue coverage. (2) When only the characteristic bands from the visible and near-infrared spectral ranges were applied, the effects of the spatial resolution differences of different images on wheat CRC had to be taken into account. The estimations of wheat CRC with the high-resolution GF-1 data were significantly better than those with the Sentinel-2 data, and among multiple machine learning algorithms adopted to estimate wheat CRC, LASSO had the most stable capability, with an R2 of 0.46 and an RMSE of 11.4%. This indicates that GF-1 high-resolution satellite imagery without shortwave infrared bands has a good potential in applications of monitoring crop residue coverage for wheat, and the relevant technology and method can also provide a useful reference for CRC estimates of other crops.
Precise fertilization of rice depends on the timely and effective acquisition of fertilizer application recommended by prescription maps in large-scale cropland, which can provide fertilization ...spatial information reference. In this paper, the prescription map was discussed based on the improved nitrogen fertilizer optimization algorithm (NFOA), using satellite and unmanned aerial vehicle (UAV) imagery, and supplemented by meteorological data. Based on the principles of NFOA, firstly, remote sensing data and meteorological data were collected from 2019 to 2021 to construct a prediction model for the potential yield of rice based on the in-season estimated yield index (INSEY). Secondly, based on remote sensing vegetation indices (VIs) and spectral features of bands, the grain nitrogen content (GNC) prediction model constructed using the Random Forest (RF) algorithm was used to improve the values of GNC taken in the NFOA. The nitrogen demand for rice was calculated according to the improved NFOA. Finally, the nitrogen fertilizer application recommended prescription map of rice in large-scale cropland was generated based on UAV multispectral images, and the economic cost-effectiveness of the prescription map was analyzed. The analysis results showed that the potential yield prediction model of rice based on the improved INSEY had a high fitting accuracy (R2 = 0.62). The accuracy of GNC estimated with the RF algorithm reached 96.3% (RMSE = 0.07). The study shows that, compared with the non-directional and non-quantitative conventional tracking of N fertilizer, the recommended prescription map based on the improved NFOA algorithm in large-scale cropland can provide accurate information for crop N fertilizer variable tracking and provide effective positive references for the economic benefits of rice and ecological benefits of the field environment.
Here we report a catalytic method for the intermolecular anti-Markovnikov hydroamination of unactivated alkenes using primary and secondary sulfonamides. These reactions occur at room temperature ...under visible light irradiation and are jointly catalyzed by an iridium(III) photocatalyst, a dialkyl phosphate base, and a thiol hydrogen atom donor. Reaction outcomes are consistent with the intermediacy of an N-centered sulfonamidyl radical generated via proton-coupled electron transfer activation of the sulfonamide N–H bond. Studies outlining the synthetic scope (>60 examples) and mechanistic features of the reaction are presented.
A challenge to the utilization of lignin as a feedstock for aromatic fine chemicals lies in selective cleavage of copious β-O-4 linkages. A photocatalytic strategy for the selective cleavage of the ...C(β)–O bonds of model substrates and natural lignin extracts is achieved by a redox-neutral, catalytic cycle that does not require stoichiometric reagents. Mechanistic studies reveal the generation of a thiyl radical, which is derived from a cystine-derived H-atom transfer catalyst, initiates a spin-center shift (SCS) that leads to C(β)–O bond cleavage. The SCS reactivity is reminiscent of the C(β)–O bond cleavage chemistry that occurs in the active site of ribonucleotide reductase.
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