Development of Immobilized Carreira (Phosphoramidite, Olefin) Ligands and Application in Iridium-Catalyzed Asymmetric Allylic Amination.

A family of polystyrene-supported (phosphoramidite, olefin) ligands L1-L4, based on the original design by Defieber and Carreira, has been developed and applied in iridium-catalyzed asymmetric allylic amination of unmasked allylic alcohols (27 examples, up to 99% ee). Among them, functional resins L1 and L4 exhibit important advantages such as easy preparation, ligand recyclability, and easy handling for sequential use. As a distinctive advantage, the catalytic use of the iridium complexes of L1 and L4 allows the straightforward reuse of a high percentage of the expensive iridium metal involved in the complexes, which is not achievable under homogeneous conditions with the corresponding monomeric complexes.

An enantio- and diastereoselective approach to indoloquinolizidines in continuous flow.

Merging polymer-supported asymmetric organocatalysis with continuous flow in a packed bed reactor has been used as the key, enantiodetermining step in a short synthesis of indoloquinolizidines. Using this approach, a highly enantioselective, solvent-free and rapid conjugate addition of dimethyl malonate to a diverse family of cinnamaldehydes in continuous flow, allowing the preparation of relevant oxodiesters in multigram amounts has been developed. The obtained Michael adducts have been used to complete an expedient diastereoselective synthesis of indoloquinolizidine via cascade Pictet-Splengler cyclisation-lactamisation in continuous flow. The conversion of enantiopure Michael adducts into δ-lactones via telescoped reduction/cyclisation in continuous flow has also been explored.

[Imaging measurement for the posterior pars interarticularis screw fixation on axis].

OBJECTIVE: To explore the safety and feasibility of posterior pars interarticularis screw fixation on axis by CT measurement. METHODS: The CT data of 137 patients with complete upper cervical spine who underwent full cervical spine CT examination from January 2016 to December 2019 were collected, including 71 males and 66 females, aged from 22 to 65 years old with an average of (41.8±17.4) years old. Mimics 19.0 software was used to measure anatomical data related to the pars interarticularis screw, including the pars width, pars vertical length, pars vertical height, length of pars screw trajectory, upward inclination angle of pars screw trajectory. And the correlation between each index was analyzed. RESULTS: The axis pars has an average width of (9.05±1.63) mm, an average vertical length of (11.21±1.43) mm, and an average vertical height of (17.53±2.93) mm. The mean length of pars screw trajectory was(19.07±3.20) mm. Regarding to the length of pars screw trajectory, 94.53% of pars measured more than 14 mm, 82.12% of pars measured at 14-16 mm, 63.14% of pars measured at 16-18 mm, 39.78% of pars measured at 18-20 mm. The upward inclination angle of pars screw was 30°-68° with an average of (46.06±8.06) °. There was a highly positive correlation between the length of screw trajectory and upward inclination angle(r=0.965, P=0.000). The vertical length of pars was weakly positively correlated with length of screw trajectory and upward inclination angle(r=0.240, P=0.000;r=0.163, P=0.007). Pars width was moderately negative correlated with length of scrwe trajectory and upward inclination angle(r =-0.333, P=0.000;r=-0.380, P=0.000). CONCLUSION: The posterior pars interarticularis screw fixation is safe and reliable. It has a more wider applicability than pedicle screw fixation and can be used as an alternative to pedicle screws.

Phosphine-Catalyzed Asymmetric Tandem Isomerization/Annulation of Allyl Amines with Allenoates: Enantioselective Annulation of a Saturated C-N Bond.

Under catalysis by chiral phosphine, an asymmetric isomerization/annulation cascade reaction of allylamines with allenoates was realized. A wide range of γ-substituted allenoates were tolerated to afford chiral pyrroline derivatives in high yields with excellent enantioselectivities. In the reaction, isomerization of readily available N-allylamines to reactive aliphatic imines through a 1,4-proton shift is a key step, which circumvents the isolation of highly unstable alkyl N-sulfonylimines.

Phosphine-Catalyzed (4 + 2) Annulation of δ-Sulfonamido-Substituted Enones with 1,1-Dicyanoalkenes: Synthesis of Piperidine Derivatives.

The δ-sulfonamido-substituted enones were employed as phosphine acceptor in phosphine-catalyzed (4 + 2) annulation of 1,1-dicyanoalkenes. They served as a four-membered synthon to react with 1,1-dicyanoalkenes under mild reaction conditions, producing piperidine derivatives in moderate to excellent yields with good to excellent diastereoselectivities.

[Wiltse approach combined with contralateral transforaminal lumbar interbody fusion and conventional surgery for lumbar disc herniation:a case-control study].

OBJECTIVE: To compare the clinical effecty of Wiltse approach combined with contralateral transforaminal lumbar interbody fusion (TLIF) and traditional TLIF in the treatment of lumbar disc herniation and its affect on injury of multifidus muscle. METHODS: From June 2014 to September 2017, 90 patients with lumbar disc herniation combined with lumbar spine instability were divided into two groups (Wiltse approach group and traditional group) depend on the procedure of operation. Wiltse approach group was treated with Wiltse approach screw placement in one side combined with contralateral TLIF. There were 50 patients in Wiltse approach group, including 36 males and 14 females, aged 45 to 72 yearswith an average of (60.4± 3.1) years. The traditional group was treated with traditional TLIF operation. There were 40 patients in the traditional group, including 25 males and 15 females, aged 45 to 74 years with an average of (62.1±3.4) years. The operative time, intraoperative blood loss, accuracy of screw implantation, postoperative drainage volume and drainage tube removal time were recorded in two groups. Visual analogue scale (VAS) and Oswestry Disability Index (ODI)were observed before and 12 months after operation. All patients underwent CT examination preoperative and 12 months postoperative, and the CT values of bilateral multifidus muscle were measured. RESULTS: All the patients were followed up, 40 patients in traditional group were 12 to 18 months with an average of (15.3±4.3) months; and 50 patients in Wiltse approach group were 13 to 24 months with an average of (16.5± 4.1) months. There were no statistically significant differences in operative time and intraoperative blood loss between two groups (P>0.05). The accuracy of screw implantation in Wiltse approach group was higher than traditional group (P<0.05).There was no significant difference in preoperative VAS score and ODI between two groups, and 12 months after operation, VAS score and ODI in Wiltse approach group was significantly lower than traditional group (P <0.05). The postoperative drainage and drainage tube placement time in Wiltse approach group were lower than the traditional group(P<0.05). There was no statistically significant difference in CT value of multifidus muscle before operation between two groups (P>0.05), while there was statistically significant difference after operation (P<0.05). Postoperative CT values of multifidus muscles on decompression and non-decompression side were obviously reduced in traditional group (P<0.05). The CT value of the multifidus muscle on the decompression side of the Wiltse approach group was significantly lower than that before operation(P<0.05), and there was no significant difference before and after the operation on the non-decompression side (P>0.05). CONCLUSION: Compared with traditional surgical procedures, the Wiltse approach nail placement combined with contralateral TLIF has the advantage of accurate nail placement, reducing multifidus muscle damage, and reducing the incidence of postoperative intractable low back pain.

Astragaloside IV suppresses transforming growth factor-ß1-induced epithelial-mesenchymal transition through inhibition of Wnt/ß-catenin pathway in glioma U251 cells.

Astragaloside IV (AS#IV) has previously demonstrated antitumoractivity. We investigated the effect and mechanisms of AS#IV in relation to epithelial-mesenchymal transition (EMT), viainterference with the Wnt/ß-catenin signaling pathway in gliomaU251 cells. Induction of glioma U251 cells by transforming growthfactor (TGF)#ß1 activated EMT, including switching E#cadherin toN-cadherin and altering the expression of Wnt/ß-catenin signalingpathway components such as vimentin, ß-catenin, and cyclin-D1.AS-IV inhibited the viability, invasion, and migration of TGF-ß1-induced glioma U251 cells. AS-IV also interfered with the TGF#ß1-induced Wnt/ß-catenin signaling pathway in glioma U251 cells.These findings indicate that AS#IV prohibits TGF#ß1-induced EMTby disrupting the Wnt/ß-catenin pathway in glioma U251 cells. AS#IV may thus be a potential candidate agent for treating glioma andother central nervous system tumors.

Phosphine-Promoted [4 + 3] Annulation of Allenoate with Aziridines for Synthesis of Tetrahydroazepines: Phosphine-Dependent [3 + 3] and [4 + 3] Pathways.

In this manuscript, phosphine-dependent [3 + 3] and [4 + 3] annulation reactions of allenoate with aziridines were disclosed. The alkyldiphenylphosphine-promoted [4 + 3] annulation of allenoate with aziridines has been achieved under mild conditions, providing biologically interesting functionalized tetrahydroazepines in moderate to excellent yield with moderate to excellent regioselectivity and diastereoselectivity.

Phosphine-Catalyzed Asymmetric Cycloaddition Reaction of Diazenes: Enantioselective Synthesis of Chiral Dihydropyrazoles.

Although carbon-carbon, carbon-nitrogen, and carbon-oxygen double bonds or their combinations have extensively been applied in phosphine-catalyzed asymmetric cycloaddition, a nitrogen-nitrogen double bond has never been investigated in chiral phosphine catalysis. In this paper, we present phosphine-catalyzed asymmetric [3+2] cycloaddition of diazenes with Morita-Baylis-Hillman (MBH) carbonates to give chiral dihydropyrazoles in high yields with excellent enantioselectivities. Various MBH carbonates and diazenes worked well under the mild reaction conditions.

A chiral squaramide-catalyzed asymmetric dearomative tandem annulation reaction through a kinetic resolution of MBH alcohols: highly enantioselective synthesis of three-dimensional heterocyclic compounds.

In this communication, a chiral squaramide-catalyzed asymmetric dearomative tandem annulation reaction of unmodified Morita-Baylis-Hillman alcohols with azomethine imines has been achieved through a kinetic resolution of MBH alcohols under mild conditions, giving pharmaceutically interesting functionalized hetero-bicyclo[3.3.1]nonane derivatives in good to excellent yields with excellent enantioselectivities.

Direct Activation of Unmodified Morita-Baylis-Hillman Alcohols through Phosphine Catalysis for Rapid Construction of Three-Dimensional Heterocyclic Compounds.

The phosphine-catalyzed tandem annulation reaction of Morita-Baylis-Hillman (MBH) alcohols with azomethine imines has been achieved for the synthesis of biologically important (epoxymethano)-pyrazolo[5,1- b]quinazoline derivatives. A variety of MBH alcohols and azomethine imines were well-tolerated under the mild reaction conditions, providing novel 3D heterocyclic compounds in high yields with excellent diastereoselectivities. It is the first time the direct activation of unmodified MBH alcohols acting as new oxa-synthons has been achieved.

Phosphine-Catalyzed [3+2] Annulation of ß-Sulfonamido-Substituted Enones with Sulfamate-Derived Cyclic Imines.

Phosphine-catalyzed [3+2] annulation of ß-sulfonamido-substituted enones and sulfamate-derived cyclic imines has been developed, giving a series of imidazoline derivatives in moderate to excellent yields with good to excellent diastereoselectivities. A scale-up reaction worked well under mild reaction conditions. A possible mechanism was proposed on the basis of the results obtained.

[Case control study of unilateral and bilateral intervertebral space release in the treatment of lower lumbar spondylolisthesis].

OBJECTIVE: To analyze the clinical efficacy of unilateral and bilateral intervertebral space release in the treatment of lower lumbar spondylolisthesis. METHODS: The clinical data of 41 patients with lumbar spondylolisthesis treated by surgery from October 2012 and May 2016 were retrospcetive analyzed. The patients were divided into two groups, 18 cases were enrolled in unilateral intervertebral release group, there were 7 males and 11 females, aged from 47 to 75 years old with an average of (59.3±6.4) years; according to Meyerding classification, 9 cases of I degree, 7 cases of II degree, 2 cases of III degree. And 23 cases were bilateral release group, there were 11 males and 12 females, aged from 51 to 76 years old with an average of (58.2±5.7) years; according to Meyerding classification, 11 cases of I degree, 10 cases of II degree, 2 cases of III degree. The operation time, intraoperative blood loss, bone graft fusion rate of the patients were recorded in the patients. Pre- and post-operative back and leg pain were evaluated by visual analogue scale (VAS) between two groups. The slip rate, slip angle, posterior height of intervertebral space, height of intervertebral foramen, distance of anterior and posterior displacement of vertex of intervertebral foramen were measured on X-ray and CT. And the above radiographic data were analyzed by intra-group or inter-group. RESULTS: All the patients were followed up from 9 to 24 months with an average of 12 months. The entire 41 patient obtained bone fusion at 12 months after operation. There was no statistical significance in VAS at 12 months after operation, intraoperative blood loss and operation time between two groups(P>0.05). There were statistical significance in sliding angle, posterior height of intervertebral space, height of intervertebral foramen, distance of anterior and posterior displacement of vertex of intervertebral foramen of all patients before and after operation(P<0.05). There was no statistical significance in spondylolisthesis rate in unilateral release group between pre- and post-operative(P>0.05), but there was significant difference in bilateral release group. There was statistical significance in postoperative slip angle, posterior height of intervertebral space, distance of anterior and posterior displacement of vertex of intervertebral foramen between two groups(P=0.001, 0.045, 0.001). The height of intervertebral foramen increased and the slippage rate decreased in both groups after operation, but there was no significant difference between two groups(P=0.248). CONCLUSIONS: Unilateral and bilateral intervertebral space release for the treatment of lumbar spondylolisthesis can obviously reduce the rate of spondylolisthesis, restore foraminal height and achieve better clinical efficacy. Bilateral release group can better restore the slip angle, increase posterior height of intervertebral space, reduce the distance of anterior and posterior displacement of vertex of intervertebral foramen. Especially for grade II or above degree of slippage is more appropriate.

Phosphine-Catalyzed [3 + 2] Annulation of 2-Hydroxy-1,4-naphthaquinones and Allenoate: An Allene-Alkene [3 + 2] Annulation Mechanism Involving Consecutive γ-Addition-Aldol Reaction.

A diastereoselective construction of biologically important tetrahydrocyclopenta[ b]naphthalene derivatives has been achieved via a phosphine-catalyzed [3 + 2] annulation of 2-hydroxy-1,4-naphthaquinone derivatives and allenoate. Various tetrahydrocyclopenta[ b]naphthalene derivatives containing contiguous quaternary carbon centers are obtained in good yields with excellent diastereoselectivities. The asymmetric version gave the chiral product in up to 57% ee under catalysis of Kwon chiral phosphine. The reaction undergoes a reaction mechanism involving consecutive γ-addition-aldol reaction.

Open reduction and internal fixation with bone grafts for comminuted mason type II radial head fractures.

BACKGROUND: The use of bone graft for the radial head fractures has been previously described and occasionally used by other authors.This is the first paper, to my knowledge, dealing with the relevant issue about the importance that the use of an autologous bone graft can have on the radial head fractures. METHODS: From July 2010 to July 2014, 20 consecutive patients who underwent open reduction and internal fixation for a closed Mason type II radial head fracture were retrospectively reviewed. Patients with Mason type I, III, simple type II, and comminuted type II fractures treated without bone grafting were excluded. A clinical examination and radiographic evaluation were performed. The overall functional result was evaluated using the Mayo Elbow Performance Score (MEPS). The Broberg and Morrey classification was used to evaluate traumatic arthritis. RESULTS: The average follow-up duration was 31 months (range, 24-50 months). Bone union of the radial head fracture was achieved in all patients at an average of 13.5 weeks (range, 12-17 weeks). Postoperative radiographs showed no cases of postsurgical ligamentous instability, necrosis of the radial head, or internal fixation failure. The mean range of motion of the affected elbow was 128° ± 8.4° in flexion, 14.5° ± 11.1° in extension, 68.7° ± 14.1° in pronation, and 65.2° ± 18.2° in supination. The mean MEPS was 92 ± 7.9 points (range, 80-100); the outcome was excellent (90-100 points) in 13 patients and good (75-89 points) in 7 patients. The MEPS tended to be higher in patients with an isolated fracture (p = 0.016). Based on the Broberg and Morrey classification for radiographic assessment of post-traumatic arthritis, 15 elbows had no evidence of degenerative changes (grade 0), and 5 elbows had grade 1 changes. CONCLUSION: Although radial head fractures may not be amenable to internal fixation, our findings suggest that open reduction and internal fixation with an autogenous bone graft from the lateral epicondyle of the humerus provides satisfactory elbow function in patients with comminuted Mason type II radial head fractures.

Phosphine-Catalyzed [8 + 2]-Annulation of Heptafulvenes with Allenoates and Its Asymmetric Variant: Construction of Bicyclo[5.3.0]decane Scaffold.

In this paper, a phosphine-catalyzed [8 + 2]-annulation of heptafulvene with allenoates has been achieved under mild conditions, giving functionalized bicyclo[5.3.0]decane derivatives in moderate to excellent yields. Using chiral phosphine as the catalyst, optically active products were obtained in moderate to high yields with excellent enantioselectivities.

Enantioselective Construction of Tetrahydroquinazoline Motifs via Palladium-Catalyzed [4 + 2] Cycloaddition of Vinyl Benzoxazinones with Sulfamate-Derived Cyclic Imines.

A palladium-catalyzed enantioselective [4 + 2] cycloaddition reaction of vinyl benzoxazinones with sulfamate-derived cyclic imines is described, affording the tetrahydroquinazolines bearing several functional rings in high yields (up to 99% yield) with good to excellent diastereoselectivities and excellent enantioselectivities (up to 96% ee). This reaction represents the first Pd-catalyzed asymmetric decarboxylative cycloaddition of vinyl benzoxazinones with imines.

Phosphine-catalyzed [5+1] annulation of δ-sulfonamido-substituted enones with N-sulfonylimines: a facile synthesis of tetrahydropyridines.

Phosphine-catalyzed [5+1] annulation of δ-sulfonamido-substituted enones with N-sulfonylimines for the synthesis of 1,2,3,6-tetrahydropyridines is developed. The reaction proceeds smoothly under mild reaction conditions to give the annulation products in moderate to excellent yields. Mechanistic exploration of this new annulation shows that the δ-sulfonamido-substituted enone and the N-sulfonylimine serve as C5 and C1 synthons to furnish the annulation, respectively. Using chiral phosphine as the catalyst, an asymmetric variant of the model reaction gave the chiral product in up to 73% ee.

Multifunctional chiral phosphine-catalyzed [3+2] annulation of Morita-Baylis-Hillman carbonates with cyclopentenones: asymmetric synthesis of 4-oxo-hexahydropentalenes.

A multifunctional chiral phosphine-catalyzed enantioselective [3+2] annulation of Morita-Baylis-Hillman carbonates with cyclopentenones provides a direct approach to access functional 4-oxo-1,3a,4,5,6,6a-hexahydropentalene compounds. Moderate to good yields and excellent enantioselectivities (>90% ee) were obtained for a series of substrates under mild reaction conditions.

Palladium-Catalyzed [5 + 2] Cycloaddition of Vinyloxiranes with Sulfamate-Derived Cyclic Imines To Construct 1,3-Oxazepine Heterocycles.

Palladium-catalyzed [5 + 2] cycloaddition of 2-aryl-2-vinyloxiranes with sulfamate-derived cyclic imines is described. The zwitterionic allylpalladium intermediates act as five-membered synthon to react with sulfamate-derived cyclic imines to furnish [5 + 2] cycloaddition, giving 1,3-oxazepine derivatives in moderate to excellent yields with excellent regioselectivities.