Synthesis of 4‑Vinylindoles Using Ruthenium-Catalyzed Ring-Closing Enyne Metathesis

The selective synthesis of substituted 4-vinylindoles by the ring-closing enyne metathesis (RCEM)/dehydration sequence is reported. In contrast with many known methods in which a pyrrole ring is constructed onto a functionalized benzene precursor, this method enables the construction of a benzene ring onto a pyrrole precursor. The RCEM/tautomerization sequence for the synthesis of 7-hydroxy-4-vinylindole is also presented as an application of this method

Catalytic Enantioselective Mannich-Type Reaction via a Chiral Silver Enolate

A catalytic asymmetric Mannich-type reaction of alkenyl trichloroacetates with aldimines was achieved using SEGPHOS·AgOTf as the chiral precatalyst and <i>N</i>,<i>N</i>-diisopropylethylamine as the base precatalyst in the presence of 2,2,2-trifluoroethanol. Optically active β-amino ketones with up to >99% ee were <i>syn</i>-selectively obtained in moderate to high yields via the in situ generated chiral silver enolates

Catalytic Enantioselective <i>N</i>-Nitroso Aldol Reaction of γ,δ-Unsaturated δ-Lactones

A catalytic asymmetric <i>N</i>-nitroso aldol reaction of γ,δ-didehydro-δ-lactones with nitrosoarenes was achieved using chiral tin dibromide as the chiral precatalyst and sodium ethoxide as the base precatalyst in the presence of ethanol. Optically active α-hydroxyamino ketones with up to 99% ee were regioselectively obtained in moderate to high yields from various δ-aryl-substituted γ,δ-didehydro-δ-valerolactones and <i>o</i>-substituted nitrosoarenes

Catalytic Enantioselective <i>N</i>-Nitroso Aldol Reaction of γ,δ-Unsaturated δ-Lactones

A catalytic asymmetric <i>N</i>-nitroso aldol reaction of γ,δ-didehydro-δ-lactones with nitrosoarenes was achieved using chiral tin dibromide as the chiral precatalyst and sodium ethoxide as the base precatalyst in the presence of ethanol. Optically active α-hydroxyamino ketones with up to 99% ee were regioselectively obtained in moderate to high yields from various δ-aryl-substituted γ,δ-didehydro-δ-valerolactones and <i>o</i>-substituted nitrosoarenes

Photograph of the fixation method for the novel primary stability test.

Photograph of the fixation method for the novel primary stability test.</p

Torque-angle curve of the lever-out test.

Uncemented acetabular shell primary stability is essential for optimal clinical outcomes. Push-out testing, rotation testing, and lever-out testing are major evaluation methods of primary stability between the shell and bone. However, these test methods do not consider shell loads during daily activity and shell installation angle. This study proposes a novel evaluation method of acetabular shell primary stability considering load during level walking and acetabular installation angles such as inclination and anteversion. To achieve this, a novel primary stability test apparatus was designed with a shell position of 40° acetabular inclination and 20° anteversion. The vertical load, corresponding to walking load, was set to 3 kN according to ISO 14242–1, which is the wear test standard for artificial hip joints. The vertical load was applied by an air cylinder controlled by a pressure-type electro-pneumatic proportional valve, with the vertical load value monitored by a load cell. Torque was measured when angular displacement was applied in the direction of extension during the application of vertical load. For comparison, we also measured torque using the traditional lever-out test. The novel primary stability test yielded significantly higher primary stabilities; 5.4 times greater than the lever-out test results. The novel primary stability test failure mode was more similar to the clinical failure than the traditional lever-out test. It is suggested that this novel primary stability test method, applying physiological walking loads and extension motions to the acetabular shell, better reflects in vivo primary stability than the traditional lever-out test.</div

Photograph of the fixation method for the lever-out test.

Photograph of the fixation method for the lever-out test.</p

Failure mode of the lever-out test.

Uncemented acetabular shell primary stability is essential for optimal clinical outcomes. Push-out testing, rotation testing, and lever-out testing are major evaluation methods of primary stability between the shell and bone. However, these test methods do not consider shell loads during daily activity and shell installation angle. This study proposes a novel evaluation method of acetabular shell primary stability considering load during level walking and acetabular installation angles such as inclination and anteversion. To achieve this, a novel primary stability test apparatus was designed with a shell position of 40° acetabular inclination and 20° anteversion. The vertical load, corresponding to walking load, was set to 3 kN according to ISO 14242–1, which is the wear test standard for artificial hip joints. The vertical load was applied by an air cylinder controlled by a pressure-type electro-pneumatic proportional valve, with the vertical load value monitored by a load cell. Torque was measured when angular displacement was applied in the direction of extension during the application of vertical load. For comparison, we also measured torque using the traditional lever-out test. The novel primary stability test yielded significantly higher primary stabilities; 5.4 times greater than the lever-out test results. The novel primary stability test failure mode was more similar to the clinical failure than the traditional lever-out test. It is suggested that this novel primary stability test method, applying physiological walking loads and extension motions to the acetabular shell, better reflects in vivo primary stability than the traditional lever-out test.</div

Schematic diagram of the polar gap measurement.

Uncemented acetabular shell primary stability is essential for optimal clinical outcomes. Push-out testing, rotation testing, and lever-out testing are major evaluation methods of primary stability between the shell and bone. However, these test methods do not consider shell loads during daily activity and shell installation angle. This study proposes a novel evaluation method of acetabular shell primary stability considering load during level walking and acetabular installation angles such as inclination and anteversion. To achieve this, a novel primary stability test apparatus was designed with a shell position of 40° acetabular inclination and 20° anteversion. The vertical load, corresponding to walking load, was set to 3 kN according to ISO 14242–1, which is the wear test standard for artificial hip joints. The vertical load was applied by an air cylinder controlled by a pressure-type electro-pneumatic proportional valve, with the vertical load value monitored by a load cell. Torque was measured when angular displacement was applied in the direction of extension during the application of vertical load. For comparison, we also measured torque using the traditional lever-out test. The novel primary stability test yielded significantly higher primary stabilities; 5.4 times greater than the lever-out test results. The novel primary stability test failure mode was more similar to the clinical failure than the traditional lever-out test. It is suggested that this novel primary stability test method, applying physiological walking loads and extension motions to the acetabular shell, better reflects in vivo primary stability than the traditional lever-out test.</div

Torque-angle curve and vertical load of the novel primary stability test.

Torque-angle curve and vertical load of the novel primary stability test.</p