Organophotoredox-Catalyzed C-H Functionalizations of Benzophospholes.

An organophotoredox-catalyzed oxidative C-H functionalization of benzophospholes has been developed. The C-H alkoxycarbonylation with methyl carbazate occurs in the presence of Rose bengal, whereas Eosin Y enables the dehydrogenative coupling with secondary phosphine oxides and ethers, delivering the C-H phosphinylated and alkylated products. The scope of coupling partners is complementary to that of conventional metal-promoted C-H activation, thus successfully expanding the chemical space of substituted phospholes accessed by C-H functionalization protocols.

Long-term results of the frozen elephant trunk technique in primary chronic type B aortic dissection.

OBJECTIVES: The aim of this study is to analyze long-term results of the total aortic arch replacement with the frozen elephant trunk technique for primary chronic type B aortic dissection. METHODS: Among 322 patients who had the frozen elephant trunk technique, 43 (13.4%) patients (median age, 64.0 years) with primary chronic type B aortic dissection were analyzed. The patients underwent surgery at a median of 27.0 months after the onset of aortic dissection. The false lumen was patent in 30 (69.8%) patients preoperatively. RESULTS: Two patients suffered paraplegia and another died of cerebral infarction. Complete thrombosis of the peri-stent false lumen was achieved in 36 (83.7%) patients. Overall survival, freedom from aortic events, and freedom from aortic reintervention were 83.5%, 37.2%, and 42.2% at 5 years, respectively. Survival rates of the patients with or without aortic events were 75.0% and 95.8% at 5 years (Log-rank, p = 0.22). Late aortic events occurred in 19 (44.2%) patients including distal stent graft-induced new entry, type Ib endoleak, and false lumen dilation. The ratio of the stent graft diameter to the preoperative short axis diameter of the true lumen (hazard ratio, 1.90; 95% confidence interval, 1.01-3.59), and the maximal diameter of a postdissection aneurysm (1.07; 1.01-1.12) were the significant multivariate risk predictors of late aortic events. CONCLUSIONS: Late aortic events occurr fairly frequently, and new strategies need to be explored to enhance the effectiveness of this procedure in the future.

Nickel-Catalyzed Electrophilic Amination of the Biphenylene C-C σ-Bond.

A nickel-catalyzed three-component carboamination of the biphenylene C-C σ-bond has been developed. Arylboronates and hydroxylamine derivatives work as carbon nucleophiles and nitrogen electrophiles, respectively, and the corresponding difunctionalized ring-opening products are obtained in good yields. The arylboronate nucleophile can be replaced with B2pin2 (boron nucleophile) and H-Si(OMe)3 (hydride nucleophile), thus allowing for the aminoboration and hydroamination of the biphenylene C-C σ-bond under similar nickel catalysis.

[Complete Disruption of the Left Main Bronchus Treated with Extracorporeal Membrane Oxygenation Support and Pneumonectomy].

A 60-year old woman, sandwiched between two boats was brought to our hospital with severe respiratory failure. She was in pre-shock and there was extensive cutaneous emphysema from the face to abdomen. She required respirator support and bilateral chest tubes for hemopneumothorax. On the patient's 3rd hospital day, she received venovenous extracorporeal membrance oxgenation( ECMO) due to sudden ventilatory failure. The bronchofiberscopy revealed complete disruption of the left main bronchus and occlusion of the right one owing to blood clot and sputum. Because of significant destruction of the left main bronchus, we didn't attempt bronchoplasty, and performed left pneumonectomy under veno-venous (VV)-ECMO. The postoperative course was uneventful, and she was discharged after 30 days with satisfactory outcome.

Development of acute hydrops in eye with infectious keratitis: A case report.

Purpose: To determine the characteristics of an eye that developed acute hydrops while being treated for infectious keratitis. Observation: A 35-year-old man presented with pain and blurred vision in his left eye. He had undergone cataract surgery seven years earlier and was being treated for poorly controlled atopic dermatitis. The decimal best-corrected visual acuity (BCVA) of the left eye was 0.01. Slit-lamp microscopy showed conjunctival injection, corneal opacification, and a corneal ulcer. The patient was diagnosed with infectious keratitis and was treated with topical and systemic antibiotics. During the hospitalization, the patient was noted to rub his eyes frequently and vigorously. Five days after the first visit, the cornea protruded markedly, and the stroma surrounding the ulcerated area was edematous. These findings led to a diagnosis of acute hydrops.Penetrating keratoplasty was performed to prevent corneal perforation. Histopathological study of the excised cornea showed stromal edema, infiltration of leukocytes, and a tear in Descemet's membrane. Unfortunately, the patient developed endophthalmitis the day after the surgery. The anterior chamber was irrigated with antibiotics, and antibiotics were also injected into the vitreous. The endophthalmitis gradually subsided, and two years after the surgery, the patient's decimal BCVA had improved to 0.6. Conclusion and importance: Vigorous eye rubbing in cases of infectious keratitis can induce acute hydrops, and timely surgical intervention is recommended.

Asymmetric Synthesis of SCF3-Substituted Alkylboronates by Copper-Catalyzed Hydroboration of 1-Trifluoromethylthioalkenes.

A synthetic method for preparation of optically active trifluoromethylthio (SCF3) compounds by a copper-catalyzed regio- and enantioselective hydroboration of 1-trifluoromethylthioalkenes with H-Bpin has been developed. The enantioselective hydrocupration of an in situ generated CuH species and subsequent boration reaction generate a chiral SCF3-containing alkylboronate, of which Bpin moiety can be further transformed to deliver various optically active SCF3 molecules. Computational studies suggest that the SCF3 group successfully controls the regioselectivity in the reaction.

Pd-catalysed C-H alkynylation of benzophospholes.

A palladium-catalysed C2-H alkynylation of benzophospholes with alkynyl bromides has been developed to afford the corresponding phosphole-alkyne conjugations in good to high yields. The C-C triple bond as well as terminal alkyne C-H bond in the obtained products is a good synthetic handle for further manipulations, thus giving the versatile π-conjugated benzophosphole derivatives. The optoelectronic properties of the newly synthesized conjugated benzophospholes are also described.

Direct synthesis of spirobifluorenes by formal dehydrative coupling of biaryls and fluorenones.

A Tf2O-mediated, direct dehydrative coupling of (hetero)biaryls and fluorenones proceeds to form the corresponding spirobifluorenes in good to high yields. The reaction system allows the relatively simple nonhalogenated and nonmetalated starting substrates to be directly adopted in the spirocyclisation reaction. In addition, the double cyclisation reaction is easily performed, giving the highly spiro-conjugated aromatic compounds of potent interest in materials chemistry. The preliminary optoelectronic properties of some newly synthesised compounds are also demonstrated.

Direct Synthesis of Benzoselenophene and Benzothiophene Derivatives from 1,1-Diarylethenes and Biaryls by Chalcogen Cation-Mediated Successive Bond Formation.

A Tf2O-mediated sequential C-Se bond-forming reaction of 1,1-diarylethenes and biaryls with methaneselenic acid has been developed. Upon demethylation workup with ethanolamine, the corresponding benzoselenophene derivatives are obtained directly. The related synthesis of benzothiophene derivatives with sodium methanesulfinate is also possible with the unique assistance of the ball milling technique. The active species is considered to be a highly electrophilic chalcogen cation, which enables successive bond formation even at room temperature.

Impact of the Barthel Index Score and Prognosis on Patients Undergoing Transcatheter Aortic Valve Replacement and Surgical Aortic Valve Replacement.

BACKGROUND: Few studies have compared the Barthel Index (BI) score and postoperative outcomes of transcatheter aortic valve replacement (TAVR) and surgical aortic valve replacement (SAVR). We aimed to examine the relationship between the BI score and postoperative outcomes in patients who underwent TAVR and SAVR.Methods and Results: The study included patients who underwent SAVR between January 2014 and December 2022 (n=293) and patients who underwent TAVR between January 2016 and December 2022 (n=312). We examined the risk factors for long-term mortality in the 2 groups. The mean (±SD) preoperative BI score was 88.7±18.0 in the TAVR group and 95.8±12.3 in the SAVR group. The home discharge rate was significantly lower in the SAVR than TAVR group. The BI score at discharge was significantly higher in the SAVR than in TAVR group (86.2 vs. 80.2; P<0.001). Significant risk factors for long-term mortality in the TAVR group were sex (P<0.001) and preoperative hemoglobin level (P=0.008), whereas those in the SAVR group were preoperative albumin level (P=0.04) and postoperative BI score (P=0.02). The cut-off point of the postoperative BI score determined by receiver operating characteristic curve analysis was 60.0. CONCLUSIONS: The BI score at discharge was a significant risk factor for long-term mortality in the SAVR group, with a cut-off value of 60.0.

Left ventricular mass and valve performance after surgical and transcatheter aortic valve replacement: a single-center experience from Japan.

Background: There are few reports on the postoperative left ventricular mass (LVM), aortic valve area (AVA), and pressure gradient (PG) after surgical aortic valve replacement (SAVR) and transcatheter aortic valve replacement (TAVR) in Japan. We aimed to compare the postoperative LVM, AVA, stroke volume (SV), PG, and long-term outcomes between patients undergoing SAVR and TAVR procedures from single center in Japan. Methods: This was a retrospective cohort study. We included 107 patients who underwent simple SAVR between January 2012 and May 2022 (SAVR group, n=107) and 274 who underwent TAVR between January 2016 and May 2022 (TAVR group, n=274). The overall mean follow-up periods was 28.8±25.9 months (median: 24 months; range, 0.03-117 months). Results: The aortic valve mean PG (mmHg) was significantly smaller in the TAVR group than in the SAVR group (P<0.001). The AVA index (cm2/m2) was significantly larger in the TAVR group than in the SAVR group (P<0.001). The SV index (mL/m2) was significantly smaller in the SAVR group than in the TAVR group (P=0.02). The LVM index (LVMI) (g/m2) was significantly smaller in the SAVR group than in the TAVR group (P<0.001). The incidence of mild or higher postoperative paravalvular leak (PVL) and pacemaker implantation were significantly higher in the TAVR group. The 5-year postoperative mortality, re-hospitalization, and major adverse cerebral and cardiovascular events (MACCEs) were significantly better in the SAVR group. Conclusions: The postoperative aortic valve PG, AVA, and SV were better in the TAVR group; however, LVM regression and postoperative outcomes were better in the SAVR group.

Stimuli-Responsive Properties on a Bisbenzofuropyrazine Core: Mechanochromism and Concentration-Controlled Vapochromism.

Stimulus-responsive organic materials with luminescence switching properties have attracted considerable attention for their practical applications in sensing, security, and display devices. In this paper, bent-type bisbenzofuropyrazine derivatives, Bent-H and Bent-sBu, with good solubilities were synthesized, and their physical and optical properties were investigated in detail. Bent-H gave three crystalline polymorphs, and they showed different luminescence properties depending on their crystal packing structures. In addition, Bent-H exhibited mechanochromic luminescence in spite of its rigid skeleton. Bent-sBu exhibited unique concentration-dependent vapochromic luminescence. Ground Bent-sBu was converted to blue-emissive, green-emissive, and green-emissive high-viscosity solution states at low, moderate, and high concentrations of CHCl3 vapor, respectively. This finding represents a concentration-dependent multi-phase transition with an organic solvent, which is of potent interest for application in sensing systems.

A Case of Autism Spectrum Disorder with Perforated Keratomalacia due to Vitamin A Deficiency.

We report a case of a patient with autism spectrum disorder (ASD) and perforated keratomalacia secondary to vitamin A deficiency. A 6-year-old boy complained of difficulty in opening the eyelids. The ocular conjunctiva was hyperemic and keratinized with purulent ocular (eye) discharge. Both corneas showed epithelial defects with hypopyon. The serum vitamin A level was ≤5 IU/dL (normal 97-316), leading to a diagnosis of xerophthalmia and keratomalacia due to vitamin A deficiency. Intramuscular injection of vitamin A (50,000 IU/day), as well as oral administration of multivitamin (containing 2,500 IU of vitamin A) and zinc supplement at 50 mg/day, allowed him to open both eyes and show interest in tablet devices 14 days after the diagnosis. During the course of the treatment, corneal perforation was observed, but it was closed without contact lens wear or amniotic patch and managed with vitamin A replacement therapy and antimicrobial eye drops. The epithelium extended to the area of the right cornea that had been melted, and although scarring corneal opacity remained, there were no obvious signs of infection. Early diagnosis is difficult because children with ASD do not express complaints, and vitamin A deficiency should be considered in patients with a severely unbalanced diet and complaints of difficulty opening the eyelids.

Rhodium-Catalyzed Isoquinoline Synthesis Using Vinyl Selenone as Oxidizing Acetylene Surrogate.

Isoquinoline is a privileged structure in many bioactive compounds and valuable ligands. Transition-metal-catalyzed oxidative annulation of imine derivatives has become a promising synthetic method; however, catalytic synthesis of 3,4-nonsubstituted isoquinolines by formal acetylene annulation has been scarce to date. Herein, we introduce vinyl selenone as an effective acetylene surrogate for the Rh-catalyzed annulative coupling under mild conditions. The Se fragment can be recovered as diselenide and recycled. The product can readily be converted to 1-aminoisoquinolines.

Surgically-treated hemoptysis and alveolar hemorrhaging resulting from severe mitral regurgitation: A case report.

Cardiac etiologies of hemoptysis are less common. One such etiology includes mitral regurgitation. In patients with hemoptysis and unilateral consolidation, careful chest auscultation and cardiac assessment may assist in making an early diagnosis.

One-Step Synthesis of Benzophosphole Derivatives from Arylalkynes by Phosphenium-Dication-Mediated Sequential C-P/C-C Bond Forming Reaction.

A metal-free, phosphenium-dication-mediated sequential C-P and C-C bond forming reaction has been developed. This protocol can provide concise access to the (di)benzophosphole derivatives in one synthetic operation from the readily available and simple arylalkynes and phosphinic acids. Application to the multiple cyclization reaction and the fully intermolecular three-component-coupling-type reaction are also described.

Synthesis of α-Aminophosphonates by Umpolung-Enabled Cu-Catalyzed Regioselective Hydroamination.

A copper-catalyzed regioselective hydroamination of α,ß-unsaturated phosphonates has been developed to form corresponding α-aminophosphonates of interest in medicinal chemistry. The introduction of an umpolung, electrophilic amination strategy with the hydroxylamine derivative is the key to achieving the α-amination regioselectivity, which is otherwise difficult under the conventional nucleophilic hydroamination conditions with the parent amine. Asymmetric synthesis with a chiral bisphosphine ligand and application to a related silylamination reaction are also described.

Open abdominal management after ruptured abdominal aortic aneurysm repair: from a single-center study in Japan.

PURPOSE: We investigated the utility of the open abdominal management (OA) technique for ruptured abdominal aortic aneurysm (rAAA). METHODS: Between January 2016 and August 2021, 33 patients underwent open surgery for rAAA at our institution. The patients were divided into OA (n = 12) and non-OA (n = 21) groups. We compared preoperative characteristics, operative data, and postoperative outcomes between the two groups. The intensive care unit management and abdominal wall closure statuses of the OA group were evaluated. RESULTS: The OA group included significantly more cases of a preoperative shock than the non-OA group. The operation time was also significantly longer in the OA group than in the non-OA group. The need for intraoperative fluids, amount of bleeding, and need for blood transfusion were significantly higher in the OA group than in the non-OA group. Negative pressure therapy (NPT) systems are useful in OA. In five of the six survivors in the OA group, abdominal closure was able to be achieved using components separation (CS) technique. CONCLUSIONS: NPT and the CS technique may increase the abdominal wall closure rate in rAAA surgery using OA and are expected to improve outcomes.

anti-Selective synthesis of ß-boryl-α-amino acid derivatives by Cu-catalysed borylamination of α,ß-unsaturated esters.

A copper-catalysed regio- and diastereoselective borylamination of α,ß-unsaturated esters with B2pin2 and hydroxylamines has been developed to deliver acyclic ß-boryl-α-amino acid derivatives with high anti-diastereoselectivity (up to >99 : 1), which is difficult to obtain by the established methods. A chiral phosphoramidite ligand also successfully induces the enantioselectivity, giving the optically active ß-borylated α-amino acids. The products can be stereospecifically transformed into ß-functionalised α-amino acids, which are of potent interest in medicinal chemistry.

Palladium-catalysed C-H arylation of benzophospholes with aryl halides.

A palladium-catalysed C-H arylation of benzophospholes with aryl halides has been developed. The reaction with aryl iodides and bromides proceeds well even under phosphine ligand-free Pd(OAc)2 catalysis whereas the Pd(PCy3)2 is effective for the coupling with less reactive aryl chlorides. The optimal conditions are also applicable to the double arylations with organic dihalides and annulation reaction with ortho-dihalogenated benzenes, making the corresponding benzophosphole-based acceptor-donor-acceptor-type molecules and highly condensed heteroacene-type molecules of potent interest in materials chemistry. Although there are many reports of catalytic C-H functionalisations of related benzoheteroles such as indoles, benzothiophenes, and benzofurans, this is the first successful example of the catalytic direct C-H transformation of benzophospholes, to the best of our knowledge. The preliminary optoelectronic properties of some newly synthesized benzophosphole derivatives are also investigated.