[Treatment of dislocation of acromioclavicular joint with TightRope fixation through a small incision in the base of coracoid process].

OBJECTIVE: To explore the method and effect of small incision TightRope fixation in the treatment of fresh acromioclavicular joint dislocation. METHODS: From January 2016 to May 2018, 28 cases of fresh acromioclavicular dislocation were treated, including 20 males and 8 females, aged 26 to 87 years with an average age of 51.3 years. The modified Rockwood classification included 1 case of typeⅡ, 22 cases of typeⅢand 4 cases of type V. The average time from injury to operation was 2.4 days. The operative time, shoulder function recovery time and postoperative complications were recorded, and the immediate reduction effect and Karlsson function of shoulder joint were evaluated. RESULTS: In 28 patients, only one Rockwood typeⅡ was used to reconstruct the pyramidal ligament, and the other 27 were used to reconstruct the pyramidal ligament and the trapezoid ligament. The average operation time was (66.50±12.62) min (including intraoperative fluoroscopy time). Twenty-eight cases were followed up for 11 to 20 (16.7±4.6) months. The recovery time of shoulder function was 2 to 7 months with an average of 4 months. During the follow-up period, 1 case had osteolysis and loss of reduction at the clavicular plate site, and the rest had no complications such as re-dislocation and button plate prolapse. Immediate reduction effect after operation:6 cases with reduction insufficiency, 17 cases with complete reduction and 5 cases with excessive reduction;Karlsson function evaluation of shoulder joint in the last follow-up:excellent in 21 cases, good in 6 cases and poor in 1 case;Pearson analysis r=0.060, suggesting that the immediate reduction effect of fresh acromioclavicular dislocation operation has no significant correlation with Karlsson function evaluationof shoulder joint in the last follow-up. CONCLUSION: TightRope fixation through a small incision in the base of coracoid process is a simple and effective method for the treatment of dislocation of acromioclavicular joint. There was no significant correlation between the slight difference of immediate reduction effect within 5 mm and Karlsson function evaluation of shoulder joint in the last follow-up. It is suggested to pay attention to the loss of reduction and osteolysis of clavicular plate in clinical follow-up.

A Pd-catalyzed asymmetric allylic substitution cascade via an asymmetric desymmetrization for the synthesis of bicyclic dihydrofurans.

A Pd-catalyzed asymmetric allylic substitution cascade of allylic meso-dicarbonates with 3-oxo-nitriles has been developed for the synthesis of chiral bicyclic dihydrofurans bearing two vicinal carbon stereocenters. The reaction proceeds via an asymmetric desymmetrization process with the desired products being obtained in high yields and with up to 97% ee. The reaction was performed on a gram-scale and the corresponding bicyclic dihydrofurans could undergo several transformations. The methodology provides an efficient synthetic route to biologically active chiral bicyclic dihydrofurans derivatives.

Selective Asymmetric Hydrogenation of Four-Membered Exo-α,ß-Unsaturated Cyclobutanones Using RuPHOX-Ru as a Catalyst.

The selective asymmetric hydrogenation of four-membered exo-α,ß-unsaturated cyclobutanones has been achieved for the first time using RuPHOX-Ru as a catalyst, providing four-membered exo-cyclic chiral allylic alcohols in high yields and with up to 99.9% ee. The reaction could be performed on a gram scale with a relatively low catalyst loading (up to 10000 S/C), and the resulting products can be transformed to several biologically active molecules.

Synthesis of Chiral α,ß-Unsaturated γ-Amino Esters via Pd-Catalyzed Asymmetric Allylic Amination.

A Pd-catalyzed asymmetric allylic amination of 4-substituted 2-acetoxybut-3-enoates with amines has been developed for the regiospecific synthesis of chiral α,ß-unsaturated γ-amino esters. The desired chiral aminated products can be obtained in up to 98% yield, and 99% ee and can be conveniently transformed to chiral γ-amino acid/alcohol derivatives and chiral γ-lactams, which can then be subjected to the synthesis of several types of chiral drugs and drug candidates. The preferential formation of chiral γ-amino esters may be attributed to the bulky substituents on the right side of the allyl substrates. This work provides an efficient strategy for the synthesis of chiral α,ß-unsaturated γ-amino esters and their derivatives.

Construction of Chiral-Fused Tricyclic γ-Lactams via a trans-Perhydroindolic Acid-Catalyzed Asymmetric Domino Reaction.

An asymmetric domino reaction was developed utilizing readily available cyclic α-dehydroamino ketones and aldehydes, which when subjected a 2-iodoxybenzoic acid (IBX)-mediated oxidation gives pyrrolidinone-containing tricyclic derivatives. trans-Perhydroindolic acid proved to be an efficient organocatalyst in this reaction (up to 94% yield, 99% ee, and >20:1 dr). The product could be conveniently converted to synthetically useful intermediates via simple transformations. A possible stereocontrolled process has been suggested according to X-ray crystallography studies.

Direct use of allylic alcohols and allylic amines in palladium-catalyzed allylic amination.

Allylic alcohols and allylic amines were directly utilized in a Pd-catalyzed hydrogen-bond-activated allylic amination under mild reaction conditions in the absence of any additives. The cooperative action of a Pd-catalyst and a hydrogen-bonding solvent is most likely responsible for its high reactivity. The catalytic system is compatible with a variety of functional groups and can be used to prepare a wide range of linear allylic amines in good to excellent yields. Furthermore, this methodology can be easily applied to the one-step synthesis of two drugs, cinnarizine and naftifine, on a gram scale.

The Construction of Chiral Fused Azabicycles Using a Pd-Catalyzed Allylic Substitution Cascade and Asymmetric Desymmetrization Strategy.

A highly enantioselective Pd-catalyzed asymmetric allylic substitution cascade of cyclic N-sulfonylimines with an accompanying asymmetric desymmetrization has been developed for the construction of fused tetrahydroindole derivatives bearing two chiral centers. Mechanistic studies confirmed that the cascade reaction proceeds by initial allylic alkylation and subsequent allylic amination. The first alkylation is a chirality-control step and represents an asymmetric desymmetrization of cis-cyclic allyl diacetates. The reaction has been performed on a gram scale, and the desired products can take part in several transformations.

Asymmetric Hydrogenation of α-Substituted Acrylic Acids Catalyzed by a Ruthenocenyl Phosphino-oxazoline-Ruthenium Complex.

Asymmetric hydrogenation of various α-substituted acrylic acids was carried out using RuPHOX-Ru as a chiral catalyst under 5 bar H2, affording the corresponding chiral α-substituted propanic acids in up to 99% yield and 99.9% ee. The reaction could be performed on a gram-scale with a relatively low catalyst loading (up to 5000 S/C), and the resulting product (97%, 99.3% ee) can be used as a key intermediate to construct bioactive chiral molecules. The asymmetric protocol was successfully applied to an asymmetric synthesis of dihydroartemisinic acid, a key intermediate required for the industrial synthesis of the antimalarial drug artemisinin.

[Design and Application of Distal Radius Anatomical Shape Bracket Splints].

OBJECTIVE: To observe the clinical effect of anatomic shape bracket splints designed by 3D-MAX software. METHODS: Healthy adult volunteers' forearms and wrist data were measured and processed by 3D-MAX software. Then we designed and made anatomic shape bracket splints. Totally 60 distal radial fracture patients were equally assigned to the test group and the control group. After manual reduction, patients in the test group used anatomic shape bracket splints, while those in the control group used common splints. The palmar dip angle, ulnar fleet angle, and radius height of standard X-ray in normal and lateral positions were measured after treatment, at 1, 3, and 6 week after treatment, respectively. Meanwhile, the incidence of complications was recorded during the whole treatment process. RESULTS: Compared with the control group, the palmar dip angle and ulnar fleet angle were larger in the test group after one week of treatment (P < 0.05). The radius height of the treatment group was higher after one, three, and six weeks of treatment (P < 0.05). Compared with the control group, the incidence of complications was obviously less in the test group (P < 0.05). CONCLUSIONS: Anatomic shape bracket splints designed by 3D-MAX software fit local anatomic features and need no more shaping. Its easier use with lesser complications could maintain the stability of bone fracture better.

Asymmetric tandem reactions of N-sulfonylimines and α,ß-unsaturated aldehydes: an alternative reaction pathway to that of using saturated aldehydes.

An organocatalyzed asymmetric tandem reaction of cyclic N-sulfonylimines and α,ß-unsaturated aldehydes was developed. These substrates follow an alternative reaction pathway to that of reactions involving saturated aldehydes, affording similar piperidine derivatives.

Asymmetric domino reaction of cyclic N-sulfonylimines and simple aldehydes with trans-perhydroindolic acid as an organocatalyst.

An asymmetric domino reaction was developed utilizing readily available cyclic N-sulfonylimines and simple aldehydes to construct biologically important and synthetically challenging piperidine derivatives consisting of three contiguous stereocenters. trans-Perhydroindolic acid proved to be an efficient organocatalyst in this reaction (up to 89% yield, 80:20 dr, and 99% ee). The absolute configuration of the catalytic product was determined by X-ray crystallography studies. The product could be conveniently converted to synthetically useful intermediates, such as (3R,4S)-4-ethyl-3-methyl-6-phenylpiperidinyridin-2-one (8), via a simple transformation.

The synthesis of chiral ß-aryl-α,ß-unsaturated amino alcohols via a Pd-catalyzed asymmetric allylic amination.

Chiral ß-aryl-α,ß-unsaturated amino alcohols were synthesized via a Pd-catalyzed asymmetric allylic amination of 4-aryl-1,3-dioxolan-2-one using planar chiral 1,2-disubstituted ferrocene-based phosphinooxazolines as ligands. Under the optimized reaction conditions, a series of substrates were examined and the products were obtained in good to excellent yields (up to 92%) and enantioselectivities (up to 98% ee) under mild reaction conditions. The desired products were determined to be of (R)-configuration and could subsequently be transformed into compounds with interesting biological activity using simple transformations.

Highly efficient asymmetric Michael addition of aldehyde to nitroolefin using perhydroindolic acid as a chiral organocatalyst.

Perhydroindolic acids, the by-products obtained in the industrial production of a trandolapril intermediate, were used as chiral organocatalysts in asymmetric Michael addition reactions of aldehydes to nitroolefins. These proline-like catalysts are unique for their rigid bicyclic structure with two H atoms attached to the bridgehead C atoms lying on the opposite side of the ring. They therefore showed high efficiency in asymmetric Michael additions of aldehydes to nitroolefins. Under the optimal conditions, excellent diastereo- and enantioselectivities (up to 99/1 dr and 98% ee) were obtained with high chemical yields for a series of aldehydes and nitroolefins using only 5 mol% catalyst loading. The methodology features easily available catalysts, high catalytic efficiency and environmentally green procedures.