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.

[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.

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.

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.

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.

Hydroamination, Aminoboration, and Carboamination with Electrophilic Amination Reagents: Umpolung-Enabled Regio- and Stereoselective Synthesis of N-Containing Molecules from Alkenes and Alkynes.

Nitrogen (N) is ubiquitously found in bioactive molecules, pharmaceutical agents, and organic functional materials. Accordingly, development of new C-N bond-forming catalysis has been one of the long-standing research subjects in synthetic organic chemistry. In this Perspective, recent advances in highly selective amination reactions with electrophilic amination reagents are described: by taking advantage of the concept of nitrogen umpolung, otherwise challenging aminofunctionalizations, such as hydroamination, aminoboration, and carboamination, of readily available feedstock-like alkenes and alkynes are possible, giving densely functionalized complex and often chiral alkylamines with high selectivity. The scope, limitations, and reaction mechanism are briefly summarized.

Palladium-Catalyzed Cross-Coupling Reaction of Diarylmethanol Derivatives with Diborylmethane.

A palladium-catalyzed cross-coupling reaction of diarylmethanol derivatives with diborylmethane has been developed. The reaction proceeds chemoselectively to deliver the corresponding homobenzylic boronates in good yields.

[To Improve the Results of Surgery for Stanford Type A Acute Aortic Dissection:Strategy for Organ Malperfusion].

OBJECTIVES: We presented the results of surgery for Stanford type A acute aortic dissection at our hospital and described strategies for organ malperfusion (especially brain malperfusion). RESULTS: From January 2012 to December 2019, we underwent 174 patients of Stanford type A acute aortic dissection at our hospital. There were 47 patients( 27.0%) with postoperative cerebral infarction (stroke group). Compared to the non-stroke group, the stroke group had significantly more cases of persistent central nervous system malperfusion before surgery and had more intraoperative bleeding and blood transfusion. The hospital mortality was 23.4% in the stroke group and 3.9% in the non-stroke group( p<0.001). As a result of multivariate analysis, risk factors for hospital mortality were preoperative endotracheal intubation, long-term cardiopulmonary bypass time and postoperative stroke. The risk factor for postoperative stroke was preoperative central nervous system malperfusion. CONCLUSIONS: As a strategy for cerebral malperfusion, it is useful to use the right axillary artery blood supply and the isolated cerebral perfusion method.

Cu-Catalyzed Reductive gem-Difunctionalization of Terminal Alkynes via Hydrosilylation/Hydroamination Cascade: Concise Synthesis of α-Aminosilanes.

A copper-catalyzed reductive gem-difunctionalization of terminal alkynes with hydrosilanes and hydroxylamines has been developed. The reaction proceeds via hydrosilylation/hydroamination cascade, and the readily available and simple terminal alkynes can be transformed into the corresponding α-aminosilanes of medicinal interest in a single operation. Additionally, the use of chiral bisphosphine ligand successfully makes the reaction enantioselective to deliver the optically active α-aminosilanes with good enantiomeric ratios.

Divergent Synthesis of Isonitriles and Nitriles by Palladium-Catalyzed Benzylic Substitution with TMSCN.

Ligand-controlled palladium-catalyzed divergent synthesis of isonitriles and nitriles from benzylic carbonates and TMSCN has been developed. The BINAP- or DPEphos-ligated palladium catalyst selectively provides the corresponding benzylic isonitriles, whereas their regioisomers, benzylic nitriles, are formed exclusively under phosphine ligand-free conditions. Mechanistic studies reveal that isonitrile is the primary product under both conditions, but it is isomerized into nitrile in the absence of ancillary phosphine ligands.

Synthesis of DPPP- and DPPPEN-Type Bidentate Ligands by Ring-Opening Diphosphination of Methylene- and Vinylcyclopropanes under Visible-Light-Promoted Photoredox Catalysis.

A ring-opening diphosphination of methylene- and vinylcyclopropanes with tetraaryldiphosphines (Ar2P-PAr2) has been developed to afford the corresponding 1,3-diphenylphosphinopropane- and 1,3-diphenylphosphinopentane-type bidentate ligands, respectively. The reaction proceeds under bromine cation-initiated, visible-light-promoted photoredox catalysis at ambient temperature. Owing to the ready availability of functionalized diphosphines, the electronically diverse MeO- and CF3-substituted bidentate ligands are also easily prepared.

Impact of the Frozen Elephant Trunk Technique on Total Aortic Arch Replacement.

BACKGROUND: The frozen elephant trunk (FET) technique can facilitate the distal anastomosis of total arch replacement (TAR); therefore, the technique is increasingly being used in TAR cases. However, identifying suitable patients remains controversial. This study analyzes the outcome of TAR using FET and clarifies the indications for using FET. METHODS: Patients who underwent TAR between January 2008 and December 2018 were enrolled and divided into 2 groups: that is, patients treated with conventional TAR (cTAR group, n = 39) and those treated with TAR using FET (TAR-FET group, n = 76). Early and late outcomes were compared. RESULTS: The mean operation time was significantly shorter in the TAR-FET group (447.0 ± 82.1 min) than in the cTAR group (509.4 ± 123.9 min) (P < 0.01). Likewise, circulatory arrest time was significantly shorter in the TAR-FET group (29.0 ± 7.8 min) than in the cTAR group (64.2 ± 20.2 min) (P < 0.001). Postoperative renal function tended to be preserved in the TAR-FET group. Recurrent nerve palsy was less frequent in the TAR-FET group (9.2%) compared with the cTAR group (25.6%) (P < 0.05). Patients with chronic aortic dissection tended to undergo reintervention more frequently following TAR using the FET technique. CONCLUSIONS: The FET technique contributed to save operation and circulatory arrest times during TAR and seemed less invasive in terms of renal function and less-frequent recurrent nerve palsy. Considering posttreatment reintervention, however, care should be taken in its application to chronic aortic dissection.

Venopulmonary artery extracorporeal lung assist in repair of traumatic aortic injury via left thoracotomy.

An urgent surgery was performed for a 28-year-old man who sustained a traumatic descending thoracic aortic injury in an automobile collision. Severe respiratory failure was encountered during surgery, which did not allow for single-lung ventilation for adequate exposure of the descending aorta. We used venopulmonary artery extracorporeal lung assist by main pulmonary artery cannulation with concurrent distal aortic perfusion using a single centrifugal pump. Cannulating the easily accessible main pulmonary artery for venopulmonary artery extracorporeal lung assist is a safe and feasible technique in patients complicated with profound respiratory failure undergoing aortic surgery via left thoracotomy.

Synthesis of Seven-Membered Benzolactones by Nickel-Catalyzed C-H Coupling of Benzamides with Oxetanes.

A NiCl2 (PEt3 )2 -catalyzed regioselective C-H coupling of 8-aminoquinoline-derived benzamides with oxetanes has been developed. The reaction proceeds with concomitant removal of the 8-aminoquinoline auxiliary to directly form the corresponding seven-membered benzolactones, which frequently occur in natural products and bioactive molecules. Additionally, no stereochemical erosion is observed during the course of the reaction, and the use of enantioenriched and substituted oxetane thus provides a new avenue to the optically active benzolactone.

Copper-Catalyzed Regio- and Enantioselective Aminoboration of Unactivated Terminal Alkenes.

A CuCl/(R,R)-PTBP-BDPP-catalyzed regioselective and enantioselective aminoboration of simple and unactivated terminal alkenes with bis(pinacolato)diboron (pinB-Bpin) and hydroxylamines has been developed. The amino group and boryl group were incorporated at the internal position and terminal position, respectively, and the corresponding chiral ß-borylalkylamines were obtained with good to high enantiomeric ratios. The asymmetric copper catalysis allows rapid and concise transformation of readily available olefinic feedstock-like materials into functionalized chiral alkylamines of high potential in medicinal and pharmaceutical chemistry.

Asymmetric Synthesis of Diarylmethyl Sulfones by Palladium-Catalyzed Enantioselective Benzylic Substitution: A Remarkable Effect of Water.

A Pd/(R)-BINAP-catalyzed enantioselective benzylic sulfonation of diarylmethyl carbonates with sodium sulfinates proceeds to deliver the corresponding chiral diarylmethyl sulfones in good yields with high enantioselectivity. The reaction occurs in a dynamic kinetic asymmetric transformation (DYKAT) manner and thus provides convergent access to optically active benzylic sulfones from racemic secondary benzylic carbonates. Additionally, the addition of H2 O is found to be critical for high enantioselectivity.

Phosphenium-Cation-Mediated Formal Cycloaddition Approach to Benzophospholes.

A phosphenium-cation-mediated formal [3+2]-cycloaddition reaction of internal alkynes is reported. The reaction proceeds under metal-free conditions to give the corresponding C-P rearranged benzophospholes regioselectively, even when ortho- and para-substituted arylphosphine oxides are starting substrates. Mechanistic studies by 31 P{1 H} NMR analysis suggest an involvement of three-membered phosphirenium cation species and C-P rearrangement prior to a ring closure for benzophosphole skeleton formation.

Synthesis of α-Aminophosphines by Copper-Catalyzed Regioselective Hydroamination of Vinylphosphines.

A copper-catalyzed net hydroamination of vinylphosphine boranes with hydrosilanes and O-benzoylhydroxylamines has been developed. The reaction proceeds regioselectively to form the corresponding α-aminophosphine boranes of potent interest in medicinal and pharmaceutical chemistry. This copper catalysis is based on an umpolung, electrophilic amination strategy and provides a new electrophilic amination approach to α-aminophosphine derivatives. Additionally, although still preliminary, asymmetric synthesis has also been achieved by judicious choice of a chiral bisphosphine-ligated copper complex.

Nickel-Catalyzed Stereospecific C-H Coupling of Benzamides with Epoxides.

A Ni(OAc)2 -catalyzed C-H coupling of 8-aminoquinoline-derived benzamides with epoxides has been developed. The reaction proceeds with concomitant removal of the 8-aminoquinoline auxiliary to form the corresponding 3,4-dihydroisocoumarins directly. Additionally, the nickel catalysis is stereospecific, and the cis- and trans-epoxides are converted into the corresponding cis- and trans-dihydroisocoumarins with retention of configuration, which is complementary to previously reported palladium catalysis. Moreover, while still preliminary, the Csp3 -H functionalization is also achieved in the presence of modified NiCl2 catalysts.