A unique and effective bypass technique to treat partially thrombosed giant distal anterior cerebral artery aneurysms in extremely narrow surgical corridors.

BACKGROUND: Surgical treatment of large or giant thrombosed anterior cerebral artery (ACA) aneurysms often involves revascularization. Herein, we describe a unique and effective bypass technique to treat partially thrombosed giant distal ACA aneurysms in extremely narrow surgical corridors. METHODS: A 68-year-old man underwent aneurysm trapping and ACA revascularization for a partially thrombosed giant ACA aneurysm in a surgical corridor that was narrow due to anatomic factors. By combining a side-to-side anastomosis and an end-to-side anastomosis at a single anastomotic site, we successfully redirected blood flow from the left pericallosal artery to the right pericallosal and callosomarginal arteries. RESULTS: Postoperatively, cerebral angiography showed that the blood flow in the aneurysm had disappeared, and the bypass remained open. The patient's functional disability gradually improved, and he reported consistently positive outcomes at the 6-month postoperative follow-up examination. CONCLUSION: This revascularization technique may represent an effective novel treatment option, particularly when multiple revascularization procedures are required within a narrow surgical field.

Factors Related to the Delayed Cure of Hemifacial Spasm after Microvascular Decompression: An Analysis of 175 Consecutive Patients.

Detailed studies assessing the factors related to delayed cure of hemifacial spasm (HFS) after microvascular decompression (MVD) are sparse. We aimed to evaluate the effect of 11 clinical factors on the time until the patient became spasm free after MVD. We enrolled 175 consecutive patients with HFS who underwent MVD between 2012 and 2018. The end point was defined as the time point at which the patient became spasm free based on the outpatient interview. Patients were divided into six groups depending on when they became spasm free after the operation, as follows: <7 days ( n = 62), 7 days to 1 month ( n = 28), 1 to 3 months ( n = 38), 3 to 6 months ( n = 25), 6 to 12 months ( n = 17), and >12 months ( n = 5). The median time to become spasm free after MVD was 30.0 days. Association of 11 factors (age, sex, laterality, number of offending arteries, vertebral artery compression, number of compression sites, compression at root detachment zone, preoperative Botox treatment, indentation of the brain stem on preoperative magnetic resonance image, transposition, and interposition) with spasm-free rate was assessed using the Cox's proportional hazards model. Spasm-free rate curve after MVD for the significant factor was obtained using the Kaplan-Meier method. In univariate and multivariate analyses, nontransposition was significantly related to delayed HFS cure after MVD (hazard ratio [HR], 0.60; 95% confidence interval [CI], 0.42, 0.87; p = 0.0068 and HR, 0.60; CI, 0.43, 0.85; p = 0.042, respectively). The spasm-free rate was higher in the transposition than in the nontransposition group ( p = 0.0013). As shortening the time until spasm free after MVD improves patients' quality of life, transposition should be recommended. Prediction of spasm-free time could relieve the anxiety of postoperative patients.

Epileptogenic zone localization using intraoperative gamma oscillation regularity analysis in epilepsy surgery for cavernomas: patient series.

BACKGROUND: In epilepsy surgery for cavernoma with intractable focal epilepsy, removal of the cavernoma with its surrounding hemosiderin deposition and other extended epileptogenic zone has been shown to improve postsurgical seizures. However, there has been no significant association between such an epileptogenic zone and intraoperative electrocorticography (ECoG) findings. The authors recently demonstrated that high regular gamma oscillation (30-70 Hz) regularity (GOR) significantly correlates with epileptogenicity. OBSERVATIONS: The authors evaluated the utility of intraoperative GOR analysis in epilepsy surgery for cavernomas. The authors also analyzed intraoperative ECoG data from 6 patients with cavernomas. The GOR was calculated using a sample entropy algorithm. In 4 patients, the GOR was significantly high in the area with the pathological hemosiderin deposition. In 2 patients with temporal cavernoma, the GOR was significantly high in both the hippocampus and the area with the pathological hemosiderin deposition. ECoG showed no obvious epileptic waveforms in 3 patients, whereas extensive spikes were observed in 3 patients. All patients underwent cavernoma removal plus resection of the area with significantly high GOR. The 2 patients with temporal cavernomas underwent additional hippocampal transection. All patients were seizure free after surgery. LESSONS: The high GOR may be a novel intraoperative marker of the epileptogenic zone in epilepsy surgery for cavernomas.

A Case Report Using Goose Neck Microsnare for Severe Cervical Internal Carotid Artery Occlusion with Dolichoarteriopathy.

Objective: We report the use of a Goose Neck microsnare for cervical internal carotid artery (ICA) occlusion in a patient with dolichoarteriopathy in whom it was difficult to achieve recanalization. Case Presentation: A 65-year-old woman underwent thrombectomy for a tandem lesion of left M1 occlusion and left cervical ICA occlusion. Recanalization of left M1 occlusion was achieved. For left cervical ICA occlusion, we attempted multiple thrombectomy using an existing device, but a hard clot with mobility was caught due to dolichoarteriopathy, which made thrombectomy difficult. Using a Goose Neck microsnare, we were able to capture the thrombus and achieve recanalization. Conclusion: Thrombectomy by capturing the thrombus using a Goose Neck microsnare may be useful for capturing hard clots with mobility when it is difficult to achieve recanalization with existing devices.

Asymmetric Synthesis of Axially Chiral Benzocarbazole Derivatives Based on Catalytic Enantioselective Hydroarylation of Alkynes.

A new synthetic approach to novel axially chiral benzocarbazole derivatives based on the highly enantioselective intramolecular hydroarylation (94-96% ee) of linked alkyne-indole systems by using the prevalent chiral base catalyst, cinchonidine or cinchonine, under unprecedented transition-metal-free conditions is described. The process is considered to involve chiral base catalysis for enantioselective transformation of the alkyne part to a reaction intermediate with an axially chiral vinylidene o-quinone methide (VQM) functionality, which subsequently effects stereospecific cyclization with the tethered indole moiety.

Vinylidene ortho-Quinone Methides: Unique Chiral Reaction Intermediates in Catalytic Asymmetric Synthesis.

Vinylidene ortho-quinone methides (VQMs) are one-carbon elongated homologues of ortho-quinone methides (QMs), well-known as useful reaction intermediates in organic transformations. These related quinone methides are quite distinct in terms of stereochemistry. Namely, VQMs are characterized by an exocyclic allenyl ketone unit merged with a dearomatized ring system and thus, can be rendered axially chiral by locating a substituent properly at the terminal methylene group of the allene moiety. It should be also noted that VQMs are tautomers of ortho-ethynylphenols and these isomeric species are correlated through a proton-shift (tautomerization). Focusing on these stereochemical and structural features, we have pursued the development of unprecedented asymmetric reactions involving enantioenriched VQM intermediates generated by chiral-base-catalyzed tautomerization of the ethynylphenol precursors. Indeed, commonly used chiral base catalysts such as cinchonine (CN) and cinchonidine (CD) have been successfully demonstrated to be effective to this end. In this account, we wish to briefly describe our recent studies on the asymmetric syntheses of optically active indeno[1,2-c]chromenes, benzofuro[3,2-b]indeno[1,2-c]chromenes, and benzo[a]carbazoles, based on the catalytic enantioselective generation of VQMs with CN or CD and the stereocontrolled intramolecular follow-up cyclization with tethered alkynes, benzofurans, and indoles, respectively.

Circular and Chainlike Copper(II)-Lanthanide(III) Complexes Generated by Assembly Reactions of Racemic and Chiral Copper(II) Cross-Linking Ligand Complexes with LnIII(NO3)3·6H2O (LnIII = GdIII, TbIII, DyIII).

The 1:1 assembly reaction of the racemic form of the cross-linking ligand complex Na[CuIILdpen(1R2R/1S2S)] with LnIII(NO3)3·6H2O gave the centrosymmetric circular (CuIILnIII)2 complex [CuIILdpen(1R2R/1S2S)LnIII(NO3)2]2 (1Ln: Ln = Gd, Tb, Dy), while the reaction of the enantiopure form Na[CuIILdpen(1R2R)] with LnIII(NO3)3·6H2O gave the chiral chainlike (CuIILnIII)1∞ complex [CuIILdpen(1R2R)LnIII(NO3)2(CH3CN)]1∞·CH3CN (2Ln: Ln = Gd, Tb, Dy), where {CuIILdpen(1R2R)}- is (N-((1R,2R)-2-(((E)-3-ethoxy-2-oxybenzylidene)amino)-1,2-diphenylethyl)-2-oxybenzamide)copper(II) and {CuIILdpen(1R2R/1S2S)}- is the racemic mixture of {CuIILdpen(1R2R)}- and {CuIILdpen(1S2S)}-. The copper(II) component functions as a cross-linking ligand complex and bridges two LnIII ions at two phenoxo oxygen atoms and one ethoxy oxygen atom, as well as at an amido oxygen atom. For 1Ln, two binuclear species of [CuIILdpen(1R2R)LnIII(NO3)2] and [CuIILdpen(1S2S)LnIII(NO3)2] with opposite chiralities are linked by two amido oxygen atoms O3 and O3* to form a centrosymmetric circular structure with Gd-Cu = 3.370(1) Å and Gd-Cu* = 5.627(1) Å. For 2Ln, binuclear species with the same chirality are bridged by Gd-O3* = 2.228(5) Å to form a chiral chainlike structure with Gd-Cu = 3.3348(9) Å and Gd-Cu* = 6.2326(9) Å. The bridged angles through the amido group of Gd-O3*═C7* are 133.9(5) and 177.6(4)° for 1Gd and 2Gd, respectively. The magnetic susceptibilities of 1Gd and 2Gd were analyzed by the spin-only Hamiltonian on the basis of the circular tetranuclear (-CuIIGdIII-)2 and linear chainlike (-CuIIGdIII-)1∞ structures, respectively. The CuII-GdIII magnetic interactions through two phenoxo bridges and a three-atom N-C═O bridge, J1 and J2, are both ferromagnetic to be J1 = +4.6 cm-1 and J2 = +1.8 cm-1 for 1Gd and J1 = +4.2 cm-1 and J2 = +0.037 cm-1 for 2Gd. The J2 value of 2Gd is much smaller than that of 1Gd. When the temperature was lowered, 1Ln and 2Ln (Ln = Tb, Dy) showed a decrease in the χMT vs T plot due to crystal field effects on the LnIII ion (Stark splitting) and an increase due to the ferromagnetic CuII-LnIII interaction. The magnetization values of 1Ln and 2Ln (Ln = Tb, Dy) without liquid paraffin are considerably larger than the corresponding values with liquid paraffin, indicating the presence of strong magnetic anisotropy. 1Tb and 1Dy showed frequency dependence of ac magnetic susceptibility under zero external dc magnetic field, showing the behavior of single-molecule magnets (SMMs). 2Tb and 2Dy showed no frequency dependence under a zero external magnetic field but showed a meaningful frequency dependence under an external magnetic field. Their energy barriers, Δ/kB, estimated by the Arrhenius plots are 29.4(6) and 20.6(3) K for 1Tb and 2Tb under dc bias fields of 0 and 1000 Oe, respectively, and those of 1Dy and 2Dy are 13.1(9) K and 16.4(2) K under dc bias fields of 0 and 1000 Oe, respectively.

Enantiospecific Aluminum-Catalyzed (3+2) Cycloaddition of Unactivated Aziridines with Isothiocyanates.

An Al(salen)Cl efficiently catalyzed the enantiospecific (3+2) cycloaddition of unactivated chiral aziridines with isothiocyanates to furnish functionalized iminothiazolidines at room temperature with 94-99% ee. The use of an aluminum Lewis acid as the catalyst, high enantiomeric purities, mild reaction conditions, broad substrate scope, and the high atom economy are the significant practical features.

Design of a robust Ru(salen) complex: aziridination with improved turnover number using N-arylsulfonyl azides as precursors.

A new robust fluorinated (OC)Ru(salen) complex was designed on the basis of an X-ray structure of its parent complex to show improved turnover numbers (up to 878) and enantioselectivities (up to 99%) in aziridination reactions using p-toluenesulfonyl (Ts) or p-nitrobenzenesulfonyl (Ns) azide as the nitrene precursor; the latter is synthetically advantageous since the Ns group is N-protecting and can be removed under mild conditions.

Zr[bis(salicylidene)ethylenediaminato]-mediated Baeyer-Villiger oxidation: stereospecific synthesis of abnormal and normal lactones.

Baeyer-Villiger oxidation of racemic bicyclic cyclobutanones with Zr[bis(salicylidene)ethylenediaminato] (salen) complex 1 as catalyst in the presence of a urea-hydrogen peroxide adduct was found to proceed enantiospecifically. The enantiotopos selection in the oxidation was governed primarily by the Zr(salen) catalyst, although migratory aptitude (methine > methylene > methyl) in Baeyer-Villiger oxidation affected the selection to a varied extent, depending on the substrate structures; one enantiomer of cyclobutanones gave exclusively a normal lactone expected from the migratory aptitude, and the other enantiomer gave an abnormal lactone preferentially, the formation of which is counter to the migratory aptitude. Furthermore, the rates of abnormal lactone formation were found to be faster than those of normal lactone formation in most of the oxidations examined. For example, the enantiomer of racemic bicyclo[3.2.0]heptan-6-one giving an abnormal lactone reacted 2.2 times faster than the other enantiomer giving a normal lactone. To our knowledge, this example of chemocatalytic Baeyer-Villiger oxidation giving an abnormal lactone in preference to a normal lactone has been previously unreported. This unusual behavior is likely to be attributable to strict control of stereoelectronic demand in Baeyer-Villiger oxidation and chiral recognition by complex 1.

Selective aerobic oxidation of hydroxy compounds catalyzed by photoactivated ruthenium-salen complexes (selective catalytic aerobic oxidation).

Selective oxidation of alcohols to the corresponding carbonyl compounds is one of the most fundamental reactions in organic synthesis. Traditional methods for this transformation generally rely on stoichiometric amount of oxidants represented by Cr(VI) or DMSO reagents, though their synthetic utility is encumbered by unpleasant waste materials. From ecological and atom-economic viewpoints, catalytic aerobic oxidation is much more advantageous because molecular oxygen is ubiquitous and the byproduct is basically non-toxic water or hydrogen peroxide. On the other hand, phenol derivatives undergo oxidative coupling, forming C-C or C-O bond, through radical intermediates coupled with an electron-transfer process. Molecular oxygen is also well known to serve as electron acceptor in this reaction. Thus, a variety of transition metal complexes have so far been examined for aerobic oxidations of alcohols and phenols, and high catalytic activities have been achieved in some cases. However, stereo- and chemo-selective aerobic oxidations are still limited in number and are of current interest. Presented in this paper is our recent studies on catalytic aerobic oxidations with photoactivated nitrosyl ruthenium-salen complexes, including asymmetric oxidation of secondary alcohols to ketones (kinetic resolution), enantioselective oxidative coupling of 2-naphthols to binaphthols and oxygen-radical bicyclization of 2,2'-dihydroxystilbene, chemoselective oxidation of primary alcohols to aldehydes and diols to lactols, and asymmetric desymmetrization of meso-diols to lactols.