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A nickel‐catalyzed reductive amidation of aryl sulfonium salts with isocyanates for amide synthesis via C−S bond cleavage was developed. The reactions proceeded smoothly at ambient temperature in the presence of nickel catalyst and manganese metal in DMF to give a variety of amides in moderate to good yields with wide functional group tolerance. [ABSTRACT FROM AUTHOR]

A tandem carbonyl reduction and hydrodefluorination of β‐trifluoromethyl enones with hydrosilanes under transition‐metal‐free conditions was developed for the synthesis of a variety of valuable gem‐difluorovinyl alcohols. The hydrosilane could act as both a reductive agent and a C(sp3)‐F bond‐breaking promoter under mild reaction conditions. Synthetically useful organofluorides, such as gem‐fluorophosphine alkene, gem‐difluorovinyl ketone, and fluorinated dihydrofuran derivatives could be readily constructed by further transformations of the obtained gem‐difluorovinyl alcohols. Moreover, the method features mild reaction conditions, operational simplicity, excellent functional group tolerance, and scalability. [ABSTRACT FROM AUTHOR]

An efficient palladium-catalyzed carbonylation of aryl fluorosulfates with aryl formates for the facile synthesis of esters was developed. The cross-coupling reactions proceeded effectively in the presence of a palladium catalyst, phosphine ligand, and triethylamine in DMF to produce the corresponding esters in moderate to good yields. Of note, functionalities or substituents, such as nitro, cyano, methoxycarbonyl, trifluoromethyl, methylsulfonyl, trifluoromethoxy, fluoro, chloro, bromo, methyl, methoxy, N,N-dimethyl, and [1,3]dioxolyl, were well-tolerated in the reactions, which could be kept for late-stage modification. The reactions employing readily available and relatively robust aryl fluorosulfates as coupling electrophiles could potentially serve as an attractive alternative to traditional cross-couplings with the use of aryl halides and pseudohalides as substrates. [ABSTRACT FROM AUTHOR]

AIM: To investigate the clinical effect of Ranibizumab combined with photodynamic therapy(PDT)for wet type age-related macular degeneration(wAMD)and the effect on the serum neovascularization factors. METHODS: Totally 68 cases(68 eyes)of wAMD patients treated with PDT in our hospital from January 2014 to June 2016 were analyzed retrospectively. Among them, 34 patients were treated by photodynamic therapy(control group)and 34 patients were treated by combination of photodynamic therapy and ranibizumab(treatment group). Comparison of BCVA, mean retinal thickness and central macular thickness(CMT)and serum neovascularization regulatory factors before and after treatment were taken between the two groups. RESULTS: Before treatment, there was no significant difference on the BCVA, the average retinal thickness and the CMT value between the two groups(P>0.05). At 3, 6 and 12mo after treatment, the BCVA, average retinal thickness and CMT in both groups were significantly lower than those before treatment(PPP>0.05). Three months after treatment, VEGF, PDGF and ES in both groups were significantly lower than those before treatment(PPCONCLUSION: The wAMD patients treated with ranibizumab combined with photodynamic therapy can achieve a more significant clinical effect, and more effectively reduce the level of serum neovascularization regulators.

A H2O-promoted and (NH4)2CO3-enabled deiodoamination and defluoroiminization reaction of fluoroalkyl alkenes has been developed under transition-metal-free conditions. Structurally important fluoroalkylated 1,5-diazapentadienes were obtained in excellent Z-selectivity with good functional group tolerance. The versatility of the method was illustrated in the synthesis of valuable organofluorides from the obtained products. Compared to traditional synthetic methods, several apparent limitations, including distillation for purification, multistep manipulation, harsh reaction conditions, moisture exclusion, and the use of toxic/sensitive reagents, could be avoided. The key to the success of the reaction is the use of (NH4)2CO3 as a commercially available, inexpensive, low-toxic, and efficient NH2/NH source and water as a C(sp3)–F bond cleavage promoter. Moreover, the distinctive fluorine effects of perfluoroalkyl substituents on substrates are also vital for enhancing the reaction efficiency. [ABSTRACT FROM AUTHOR]

AIM: To investigate the correlation of matrix metalloproteinase -9(MMP-9), glycated albumin(GA), glycosylated hemoglobin(HbA1c)and adipokines(including visfatin, resistin and leptin)with diabetic retinopathy(DR). METHODS: From March 2015 to March 2017, 74 patients with DR were treated in our hospital, including 40 patients(80 eyes)with non proliferative diabetic retinopathy(NPDR)and 34 patients(68 eyes)with proliferative diabetic retinopathy(PDR), and diabetes mellitus 40 patients(80 eyes)with non DR(NDR)and 40 healthy volunteers(80 eyes)were selected as controls, the levels of MMP-9, GA, HbA1c, visfatin, resistin and leptin in each group were detected. RESULTS: PDR group visfatin was 4.41±0.82ng/mL, was significantly lower than the NPDR group, NDR group and control group(PPPPrs=0.523, 0.461 and 0.414, Prs=-0.433, Prs=0.401 and 0.460, PCONCLUSION: MMP-9, GA, HbA1c, and adipokines may play a role in the development and progression of DR, in which MMP-9 is associated with adipokines, both are not significantly related to the levels of GA and HbA1c.

The distinctive hydrophobic hydration effect in the aqueous solution contributes to the success of the phospha‐Michael reaction between β‐CF3‐β,β‐disubstituted enones and diarylphosphine oxides, providing an access to biologically relevant γ‐ketophosphine oxides bearing a sterically highly congested CF3‐ and P(O)‐tetrasubstituted carbon center. More importantly, the resulting products could be further transformed into densely functionalized γ‐ketophosphine oxides containing a CF3‐ and P(O)‐tetrasubstituted carbon center. [ABSTRACT FROM AUTHOR]

An aerobic coupling of benzhydryl phosphonium salts with simple alkenes for accessing trisubstituted olefins is developed under metal‐free, catalyst‐free, and additive‐free conditions. New C(sp3)−C(sp2) bond is constructed via the C−P and C−H bond functionalization by synergistically using O2 as a "green" oxidant and DMSO as a promoter. The method also distinguishes itself by its broad substrate scope and synthetic potential. Particularly, the use of 1,3,5‐trimethoxybenzene fragment in the resulting products as a carbon‐based leaving group for further transformations is proved to be feasible. [ABSTRACT FROM AUTHOR]