Hydrosilylation and Mukaiyama aldol-type reaction of quinolines and hydrosilylation of imines catalyzed by a mesoionic carbene-stabilized borenium ion.

Aldimines and ketimines containing electron-donating and electron-withdrawing groups can be hydrosilylated with borenium catalysts at as low as 1 mol% catalyst loading at room temperature, providing the corresponding secondary amines in excellent yields. Reactions with 2-phenylquinoline gave the 1,4-hydrosilylquinoline product selectively which can be further functionalized in a one-pot synthesis to give unique γ-amino alcohol derivatives. Control experiments suggest that the borenium ion catalyzes both the hydrosilylation and subsequent addition to the aldehyde.

Arynes and Their Precursors from Arylboronic Acids via Catalytic C-H Silylation.

A new, operationally simple approach is presented to access arynes and their fluoride-activated precursors based on Ru-catalyzed C-H silylation of arylboronates. Chromatographic purification may be deferred until after aryne capture, rendering the arylboronates de facto precursors. Access to various new arynes and their derivatives is demonstrated, including, for the first time, those based on a 2,3-carbazolyne and 2,3-fluorenyne core, which pave the way for novel derivatizations of motifs relevant to materials chemistry.

Ru-catalysed C-H arylation of indoles and pyrroles with boronic acids: scope and mechanistic studies.

The Ru-catalysed C2-H arylation of indoles and pyrroles by using boronic acids under oxidative conditions is reported. This reaction can be applied to tryptophan derivatives and tolerates a wide range of functional groups on both coupling partners, including bromides and iodides, which can be further derivatised selectively. New indole-based ruthenacyclic complexes are described and investigated as possible intermediates in the reaction. Mechanistic studies suggest the on-cycle intermediates do not possess a para-cymene ligand and that the on-cycle metalation occurs through an electrophilic attack by the Ru centre.

Boryl (Hetero)aryne Precursors as Versatile Arylation Reagents: Synthesis through C-H Activation and Orthogonal Reactivity.

(Pinacolato)boryl ortho-silyl(hetero)aryl triflates are presented as a new class of building blocks for arylation. They demonstrate unique versatility by delivering boronate or (hetero)aryne reactivity chemoselectively in a broad range of transformations. This approach enables the unprecedented postfunctionalization of fluoride-activated (hetero)aryne precursors, for example, as substrates in transition-metal catalysis, and offers valuable new possibilities for aryl boronate postfunctionalization without the use of specialized protecting groups.

Do expandable cage size and number of cages matter in transforaminal lumbar interbody fusion at L5-S1? A comparative biomechanical analysis using finite element modeling.

OBJECTIVE: Expandable transforaminal lumbar interbody fusion (TLIF) cages were designed to address the limitations of static cages. Bilateral cage insertion can potentially enhance stability, fusion rates, and segmental lordosis. However, the benefits of unilateral versus bilateral expandable cages with varying sizes in TLIF remain unclear. This study used a validated finite element spine model to compare the biomechanical properties of L5-S1 TLIF by using differently sized expandable cages inserted unilaterally or bilaterally. METHODS: A finite element model of X-PAC expandable lumbar cages was created and used at the L5-S1 level. This model had cage dimensions of 9 mm in height, 15° in lordosis, and varying widths and lengths. Various placements (unilateral vs bilateral) and sizes were examined under pure moment loading to evaluate range of motion, adjacent-segment motion, and endplate stress. RESULTS: Stability at the L5-S1 level decreased when smaller cages were used in both the unilateral and bilateral cage models. In the unilateral model, cage 1 (the smallest cage) resulted in 47.9% more motion at the L5-S1 level compared to cage 5 (the largest cage) in flexion, as well as 64.8% more motion in extension. Similarly, in the bilateral TLIF model, bilateral cage 1 led to 49.4% more motion at the L5-S1 level in flexion and 73.4% more motion in extension compared to bilateral cage 5. Unilateral insertion of cage 5 provided superior stability in flexion and surpassed cages 1-3 in extension when compared to cages inserted either unilaterally or bilaterally. Reduced motion at L5-S1 correlated with increased adjacent-segment motion at L4-5. Bilateral TLIF resulted in greater adjacent-segment motion compared to unilateral TLIF with the same-size cages. Inferior endplates experienced higher stress during flexion and extension than superior endplates, with this difference being more pronounced in the bilateral model. In bilateral cage placement, stress differences ranged from 46.3% to 60.0%, while they ranged from 1.1% to 9.6% in unilateral cages. Qualitative analysis revealed increased focal stress in unilateral cages versus bilateral cages. CONCLUSIONS: The authors' study shows that using a large unilateral TLIF cage may offer better stability than the bilateral insertion of smaller cages. While large bilateral cages increase adjacent-segment motion, they also provide a uniform stress distribution on the endplates. These findings deepen our understanding of the biomechanics of the available expandable TLIF cages.

Comparative Biomechanical Analysis of Anterior Lumbar Interbody Fusion and Bilateral Expandable Transforaminal Lumbar Interbody Fusion Cages: A Finite Element Analysis Study.

BACKGROUND: Expandable transforaminal lumbar interbody fusion (TLIF) cages could offer an alternative to anterior lumbar interbody fusion (ALIF). Bilateral cage insertion enhances endplate coverage, potentially improving stability and fusion rates and maximizing segmental lordosis. This study aims to compare the biomechanical properties of bilateral expandable TLIF cages to ALIF cages using finite element modeling. METHODS: We used a validated 3-dimensional finite element model of the lumbar spine. ALIF and TLIF cages were created based on available product data. Our focus was on analyzing spinal motion in the sagittal plane, evaluating forces transmitted through the vertebrae, and comparing an ALIF model with various TLIF cage models. RESULTS: The largest TLIF cage model exhibited a 407.9% increase in flexion motion and a 42.1% decrease in extension motion compared with the ALIF cage. The second largest TLIF cages resulted in more flexion motion and less extension motion compared with ALIF, while smaller cages were inferior to ALIF. ALIF cages were associated with increased adjacent segment motion compared with TLIF cages, primarily in extension. Endplate stress analysis revealed higher stress in the ALIF cage model with a more uniform stress distribution. CONCLUSION: ALIF cages excel in stabilizing L5 to S1 during flexion, while largest TLIF cages offer superior stability in extension. Large bilateral TLIF cages may provide biomechanical stability comparable to ALIF, especially in extension and could potentially reduce the risk of adjacent segment disease with lower adjacent segment motion.

Using Finite Element Models to Assess Spinal Cord Biomechanics after Cervical Laminoplasty for Degenerative Cervical Myelopathy.

Cervical laminoplasty is an established motion-preserving procedure for degenerative cervical myelopathy (DCM). However, patients with pre-existing cervical kyphosis often experience inferior outcomes compared to those with straight or lordotic spines. Limited dorsal spinal cord shift in kyphotic spines post-decompression and increased spinal cord tension may contribute to poor neurological recovery and spinal cord injury. This study aims to quantify the biomechanical impact of cervical sagittal alignment on spinal cord stress and strain post-laminoplasty using a validated 3D finite element model of the C2-T1 spine. Three models were created based on the C2-C7 Cobb angle: lordosis (20 degrees), straight (0 degrees), and kyphosis (-9 degrees). Open-door laminoplasty was simulated at C4, C5, and C6 levels, followed by physiological neck flexion and extension. The results showed that spinal cord stress and strain were highest in kyphotic curvature compared to straight and lordotic curvatures across all cervical segments, despite similar segmental ROM. In flexion, kyphotic spines exhibited 103.3% higher stress and 128.9% higher strain than lordotic spines and 16.7% higher stress and 26.8% higher strain than straight spines. In extension, kyphotic spines showed 135.4% higher stress and 241.7% higher strain than lordotic spines and 21.5% higher stress and 43.2% higher strain than straight spines. The study shows that cervical kyphosis leads to increased spinal cord stress and strain post-laminoplasty, underscoring the need to address sagittal alignment in addition to decompression for optimal patient outcomes.

Effect of sagittal alignment on spinal cord biomechanics in the stenotic cervical spine during neck flexion and extension.

Spinal cord stress and strain contribute to degenerative cervical myelopathy (DCM), while cervical kyphosis is known to negatively impact surgical outcomes. In DCM, the relationship between spinal cord biomechanics, sagittal alignment, and cord compression is not well understood. Quantifying this relationship can guide surgical strategies. A previously validated three-dimensional finite element model of the human cervical spine with spinal cord was used. Three models of cervical alignment were created: lordosis (C2-C7 Cobb angle: 20°), straight (0°), and kyphosis (- 9°). C5-C6 spinal stenosis was simulated with ventral disk protrusions, reducing spinal canal diameters to 10 mm, 8 mm, and 6 mm. Spinal cord pre-stress and pre-strain due to alignment and compression were quantified. Cervical flexion and extension were simulated with a pure moment load of 2 Nm. The Von Mises stress and maximum principal strain of the whole spinal cord were calculated during neck motion and the relationship between spinal cord biomechanics, alignment, and compression was analyzed using linear regression analysis. Spinal cord pre-stress and pre-strain were greatest with kyphosis (7.53 kPa, 5.4%). Progressive kyphosis and stenosis were associated with an increase in spinal cord stress (R2 = 0.99) and strain (R2 = 0.99). Cervical kyphosis was associated with greater spinal cord stress and strain during neck flexion-extension and the magnitude of difference increased with increasing stenosis. Cervical kyphosis increases baseline spinal cord stress and strain. Incorporating sagittal alignment with compression to calculate spinal cord biomechanics is necessary to accurately quantify spinal stress and strain during neck flexion and extension.